Tesis 460VFordenlectura

Departamento de Geología y Geoquímica
January 2012
Difusión de contaminantes en
vertederos antiguos construidos en
terrenos arcillosos
Diffusion of pollutants
in old landfills built
over clayey substrata
Mercedes Regadío García
PhD Thesis
Difusión de contaminantes en
vertederos antiguos construidos
en terrenos arcillosos
Tesis doctoral presentada a la Universidad Autónoma de Madrid, Facultad de

Ciencias, Departamento de Geología y Geoquímica para optar al grado de Doctor.
Madrid, Diciembre 2011.
Mercedes Regadío García. Director: Dr. Jaime Cuevas Rodríguez.
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis | III
Difusión de contaminantes en vertederos antiguos construidos en terrenos arcillosos
Tesis doctoral, enero 2012
La tesis estará disponible en versión pdf en la página web de la biblioteca de Ciencias, de la

Universidad Autónoma de Madrid: http://biblioteca.uam.es/
Dirección: Universidad Autónoma de Madrid

Facultad de Ciencias
C/ Fco. Tomás y Valiente 7
28049 Madrid, España
Teléfono: (+34) 91 497 48 00
Fax: (+34) 91 497 49 00
Página web: http://www.uam.es/departamentos/ciencias/geolgeoq/

Department of Geology and Geochemistry
Diffusion of pollutants in old

landfills built over clayey
substrata
A thesis submitted to Autónoma University of Madrid, Faculty of Science,

Department of Geology and Geochemistry in partial fulfilment of the requirements
for the degree of Doctor of Philosophy.
Madrid, December 2011.
Mercedes Regadío García. Supervisor: Dr. Jaime Cuevas Rodríguez.
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis | V
Diffusion of pollutants in old landfills built over clayey substrata
PhD thesis, January 2012
The thesis will be available as a pdf-file from the homepage of the library of Sciences, of
the Autónoma University of Madrid: http://biblioteca.uam.es/
Adress: Autónoma University of Madrid

Faculty of Sciences
Departament of Geology and Geochemistry
C/ Fco. Tomás y Valiente 7
28049 Madrid, Spain
Telephone: (+34) 91 497 48 00
Fax: (+34) 91 497 49 00
Homepage: http://www.uam.es/departamentos/ciencias/geolgeoq/
Este trabajo ha sido financiado por el Ministerio de Medio Ambiente, Rural y Marino
(MMA: I+D+i A113/2007/3_02.6) en cooperación con Geotecnia y Cimientos S.A.
(GEOCISA) y el Centro de Experimentación de Obras Públicas (CEDEX).
This work was funded by the Spanish Environmental Ministry (MMA: I+D+i
A113/2007/3_02.6) in cooperation with Geotecnia y Cimientos S.A. (GEOCISA) and
the Centro de Experimentación de Obras Públicas (CEDEX).
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis | VII
De todo corazón:
A mi madre, a mi padre y a mi hermano.
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis | IX
“Waste is a tax on the whole people”
Albert W. Atwood
“Take care of the earth and she will take care of you”
Unknown Author
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis | XI
PREFACE
This PhD thesis, entitled Diffusion of pollutants in old landfills built over clayey substrata, is
based on research undertaken from November 2007 to September 2011 at the Department of
Geology and Geochemistry, Autónoma University of Madrid (UAM). The work was done
under the supervision of Professor Jaime Cuevas Rodríguez and was funded through a
national research project of the Spanish Environmental Ministry.
The investigation was primarily carried out at UAM, but included collaboration from
Geotecnia y Cimientos S.A. (GEOCISA) and the Centro de Experimentación de Obras
Públicas (CEDEX). Additionally, one external stay at the Department of Mineralogy, in the
Natural History Museum of London, under the charge of Dr. Javier Cuadros, was performed
between June and September of 2010.
At the time of writing, one scientific journal paper based on this study* (Appendix X) has
been accepted to publish. Future articles about the content of the thesis are going to be
summited in the next years.
In addition, the following reports, publications and conference proceedings related to the
topic of the thesis, have been co-authored during the PhD-study, and some of them will also
be referred to in the thesis:
PROJECT REPORTS
GEOCISA & UAM (2010). Final Project Report: “La difusión de contaminantes en las
barreras de vertederos urbanos y su evolución en el tiempo”. Proyect I+D+i - A.
Ref. n. 113/2007/03-02.6, Ministerio de Medioambiente, Rural y Marino, Gobierno
de España:224.
SCIENTIFIC PUBLICATIONS
* Regadío, M.; Ruiz, A.I.; de Soto, I. S.; Rastrero, M. R.; Jiménez, N. S.; Gismera,
M.J.; Sevilla, M.T.; da Silva, P.; Procopio, J. R.; Cuevas. J. (2012). Pollution
profiles and physicochemical parameters in old uncontrolled landfills. Waste
management, 32: 483-498. DOI:10.1016/j.wasman.2011.11.008.
Cuevas, J.; Ruiz, A.I.; de Soto, I.S.; Sevilla, M.T.; Procopio, J.R.; da Silva, P.; Gismera,
M.J.; Regadío, M.; Jiménez, N. S.; Rastrero, M. R.; Leguey, S. (2011). The
performance of natural clay as a barrier to the diffusion of municipal solid waste
landfill leachates. Journal of Environmental Management. DOI:
10.1016/j.jenvman.2011.02.014.
Ruiz, A.I.; de Soto, I. S.; Jiménez, N. S.; Regadío, M; Fernández, R; Cuevas, J. (2011).
Improvement of attenuation functions of a clayey sandstone for landfill leachate
containment by bentonite addition. Science of the Total Environment. DOI:
10.1016/j.scitotenv.2011.11.054
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis | XIII
de Soto, S. I.; Ruiz, A.I.; Ayora, C.; García, R.; Regadío, M.; Cuevas; J. Diffusion of a
model landfill leachate through natural compacted clays containing small amounts
of smectite. Applied geochemistry, (under review).
CONFERENCE PROCEEDINGS
Regadío, M.; Ruiz, A. I.; de Soto, I. S.; Rastrero, M. R.; Jiménez, N. S.; Gismera, M. J.;
Cuevas, J. Attenuation and characteristics of urban landfill pollutants over clayey
substrata. VIII Iberian Geochemistry Congress, XVII Geochemistry.
Sep 24-28, 2011 Quinta da Senhora de Mércules, Portugal
Ruiz, A.I.; de Soto, I.S.; Jiménez, N. S.; Regadío, M.; Fernández, R.; Cuevas, J.
Ammonium chloride transport through different natural clay barriers. Trilateral
Meeting on Clays Jun 6-11, 2010 Seville, Spain
Ruiz, A.I.; Regadío, M.; de Soto, I.S.; Rastrero, M. R.; Jiménez, N. S.; Gismera, M.J.;
Cuevas, J. Pollution profiles of old urban landfills built over clays. VII Iberian - X
National Geochemistry Congress Sep 21-23, 2009 Soria, Spain
Ruiz, A.I.; Rastrero, M. R.; Regadío, M.; de Soto, I.S.; Jiménez, N. S.; Sevilla, M.T.;
Procopio, J. R.; Gismera, M.J.; da Silva, P.; Leguey, S.; Cuevas, J. Pollution
migration in old urban landfills emplaced upon clays. XIV International Clay
Conference Jun 14-20, 2009 Castellaneta Marina, Italy
Cuevas, J.; Sevilla, M.T.; Procopio, J. R.; Ruiz, A.I.; da Silva, P.; Gismera, M.J.; Regadío,
M.; Jiménez, N. S.; de Soto, I.S.; Rastrero, M. R.; Leguey, S. An integrated
approach to natural and geosynthetic clay barriers performance against the
diffusion of a pollution plume from municipal solid waste (MSW) landfills. III
International Meeting on Environmental Biotechnology & Engineering Sep 21-25,
2008 Palma Mallorca, Spain
Regadío, M.; Cuevas, J.; Gismera, M.J.; Leguey, S.; Procopio, J. R.; Rastrero, M. R.; Ruiz,
A.I.; Jiménez, N. S.; Sevilla, M.T.; da Silva, P.; de Soto, I.S. Study of the pollution
in landfills built over clays. XXVIII Meeting of the Spanish Mineralogical Society,
XXI Meeting of the Spanish Clay Society Sep 15-19, 2008 Zaragoza, Spain
Mercedes Regadío García.
XIV | Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis
AGRADECIMIENTOS
Ahora, es cuando me doy cuenta, de lo difícil que es reflejar en unas líneas todo el apoyo
recibido durante la realización de este trabajo y que significó tanto para mí.
La presente tesis no hubiera sido igual sin la orientación, comentarios y aclaraciones de

Jaime Cuevas, los cuáles han resultado de gran utilidad. Las conversaciones y los emails que
hemos intercambiado, sin duda han jugado un importante papel en el contenido final de la
tesis. Debo agradecer a Jaime, su valiosa ayuda y tutela en mis primeros pasos hacia la
investigación sobre la problemática de los vertederos y las aplicaciones que ofrecen las
arcillas. Sus consejos prácticos y personales me han valido para afrontar las distintas etapas
de este trabajo y espero que en el futuro podamos seguir trabajando en proyectos comunes.
Asimismo, quiero agradecer a Isabel de Soto su predisposición a resolver mis dudas

sobre el tedioso procedimiento burocrático que envuelve la tesis. No puedo imaginar una
mejor compañera de laboratorio, docencia, comidas y descansos. También he tenido mucha
suerte en compartir laboratorio y despacho con Manuel Rodríguez y José Gumuzzio. Ellos,
junto con Santiago Leguey, Raquel Vigil y Rosario García me han proporcionado los
empujones iniciales necesarios para inspirarme. Sin olvidar los ánimos y consejos dados por
Amalia Álvarez, Ana Ruiz, Almudena Ortega, Juan Limia, Raúl Fernández y Óscar Ríos,
¡muchas gracias! Igualmente, deseo dar las gracias a Gonzalo Alonso (y sus valiosas
lecciones de preparación de láminas delgadas) y al resto del personal que formaron y que
forman parte del departamento de Geología y Geoquímica.
Deseo destacar la colaboración del departamento de Química Analítica y Análisis

Instrumental, concretamente de M. Jesús Gismera, Maite Sevilla, Pilar da Silva, Nicanor
Sánchez y Jesús Rodríguez; así como el apoyo tanto técnico como humano prestado por
Pedro Avellanosa, Alfredo Álvarez y Juan Manuel Rogel (GEOCISA). Gracias a Xavier
Rubio i Llambí y Beatriz González por ayudarme a completar mis pesquisas acerca de los
vertederos Z4V1 y Z1V1. Y también mis agradecimientos a Javier Cuadros por darme la
oportunidad de realizar una estancia con él y guiarme en los análisis de DRX, FTIR y CNH.
De forma especial, quisiera reconocer la labor social, ambiental y solidaria de Amigos

de la Tierra, organización que conozco desde hace años. Y también agradecer a Goteo
Cultura Sostenible por cuidar de mi bici, después de algún que otro incidente.
Y gracias a mis amigos de Lugo, de Monte, del Juan Luis Vives y de Ciencias
Ambientales que, de una forma u otra, han influido en mis ánimos, mis decisiones, mis idas y
venidas. Gracias a las más veteranas: a Laura, por su predisposición a “cafelitos” y “post-
cafelitos”; a Tamara, por poder contar con ella en los planes que nadie se atreve a
apuntarse; y a Stella, por las conversaciones desinhibidas. Aprecio también el tiempo
dedicado por Carlos a ayudarme con el LaTeX, aunque finalmente lo utilizara en otros
trabajos.
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis | XV
Y, por supuesto, mil gracias a mi familia, que ha hecho una labor heroica y me han
acompañado de numerosas formas, de modo constante y más personal, a lo largo de mi vida.
Para mí, ellos son los verdaderos protagonistas.
Gracias a todos.
Mercedes Regadío.
XVI | Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis
Calendar 2012
Z4V1: Cataluña landfill

(23 years, 3 ha)
Z6V1: Madrid landfill 1
(24 years, 20 ha)
Z6V2: Madrid landfill 2
(13 years, 36 ha)
Z1V1: Cantabria landfill
(9 years, 10 ha)
Z5V1: Andalucía landfill
(14 years, 30 ha)
ZXVXL: Leachate from ZXVX landfill
L1: leachate of deionized water

L2: methanogenic synthetic leachate
L3: acetogenic synthetic leachate
L4: methanogenic real leachate
(El Garraf landfill)
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis | XVII
XVIII | Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis
ABSTRACT
An appropriate disposal of waste in landfills is a key issue for protecting, preserving and
improving the environment and the human health. The most applied policy for landfilling is the
containment strategy (complete isolation of the deposited waste by means of bottom and top liner
systems and collection of gas and leachate emissions combined with everlasting aftercare
monitoring). Under these conditions, the waste itself remains a source of pollution and the
problem is not solved, since if something accidentally fails, the pollutants will be released. For
that reason, more and more importance is being attached to the attenuation strategy (included in
“the multibarrier concept” and the European legislation). This strategy considers the landfill and
geological barrier”)
the underlying natural substratum (“geological barrier as a biochemical reactor in which natural
processes (dilution, dispersion, biodegradation, filtration, redox, precipitation, sorption or ionic
exchange reactions) take place and reduce and eliminate the contamination.
In the present thesis, the response of natural and common Spanish clayey soils to leachate
solutions in the long term is investigated both: (i) under a real approach with soil samples below
five actual municipal wastes (MW) landfill sites (9-24 years old and no engineered liners) and (ii)
under a laboratory approach based on a four-year diffusion experiment with a natural clay
compacted in four 0.5 m-height columns; each one in contact with a different leachate. More
than 30 parameters were measured in the clayey samples at different depths: physicochemical
parameters (electrical conductivity, EC; redox potential, Eh; pH, water soluble organic and
inorganic carbon, WSOC/WSIC; ions, alkalinity…) and geological parameters (exchangeable
cations, Ex_cat; cationic exchange capacity, CEC; moisture, h; specific surface area, SSA;
mineralogy, microfabric, density). The important quantity of data made it necessary to perform
statistical procedures in order to (i) observe correlations within the measured parameters and
between them and the attenuation of leachate pollutants (principal component analysis and
Varimax rotation) and (ii) to know what effects caused by the different types of leachates on the
parameters measured in the clayey materials, are significant (multivariate analysis of variance,
between-effects and multivariate tests).
Although leachates have been in contact with clays for long periods of time, the main soluble
components of leachates were attenuated (concentration decrease 90-100%) at depths of only
≤1.5 m from the waste/soil contact within the clay layer. The ratio decrease per meter depth (Dm)
and a diffusive flux attenuation capacity (Ac) were defined for each natural substratum to study
the differences between them and to compare their performance as a barrier, under normalized
conditions of leachate exposure time and quantity of waste per area.
The most suitable materials were those with ≥47% sheet silicates, characterized by a ratio of
illite/smectite between 1.8 and 5, with carbonates and high SSA and density. The observed
attenuation depths and the estimated hydraulic conductivity (K) in the studied natural materials
proved that the minimum depth and the maximum K of a geological barrier established by
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis | XIX
Directive 1999/31/EC (1999) are adequate for the pollution control of major soluble species in
the leachate. NH4+ was the most indicative parameter of the penetration of landfill leachate
pollution and it was effectively retained by exchange reactions. Such ion exchange capacity is
interesting for environmental remediation in contaminated sites. The important roles, in the
retardation mechanisms, of water entry, sorption, biodegradation, pH buffer capacity, nature of
wastes, types of clays, matrix diffusion and precipitation-dissolution equilibrium, have also been
discussed.
Consequently, the long-term effectiveness of several geological barriers beneath MW landfills

was analyzed in detail and reliable data relevant to design natural attenuation strategies were
presented. The attenuation strategy leads to a more sustainable and more cost-effective waste
management concerning (i) liners installation, (ii) drainage and gas collection systems and (iii)
post-closure monitoring. Therefore, this strategy results in a more affordable technology for
developing countries, where water diseases related to waste pollution kill millions of people,
mostly children, per year.
KEYWORDS
Landfills, clays, depth profiles of parameters, natural attenuation.
XX | Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis
RESUMEN
Un vertido de residuos adecuado es una cuestión clave para la protección, conservación y mejora
del medio ambiente y la salud humana. La política de vertederos más aplicada es la estrategia de
contención (completo aislamiento de los residuos depositados por medio de una barrera artificial
inferior y superior y la recolección de las emisiones de gases y lixiviados en combinación con una
vigilancia postratamiento permanente). Bajo estas condiciones, los propios residuos siguen siendo
una fuente de contaminación y el problema no se resuelve, ya que si accidentalmente algo falla,
los contaminantes se liberarían. Por esta razón, se está considerando cada vez más la estrategia de
atenuación (incluida en el “concepto multibarrera”, recogido en la legislación europea, entre
barrera geológica")
otras). Esta estrategia considera el propio sustrato natural subyacente ("barrera geológica como
un reactor bioquímico en el que los procesos naturales (dilución, dispersión, biodegradación,
filtración, precipitación, rédox, adsorción o reacciones de intercambio iónico) se encargan de
reducir y eliminar la contaminación.
La presente tesis investiga la respuesta a largo plazo de distintas arcillas naturales

representativas de España, al contacto directo con lixiviados de vertederos, desde dos actividades:
(i) bajo un enfoque real; con muestras de suelo recogidas bajo cinco vertederos de residuos
urbanos (RU), entre 9 y 24 años de edad y en zonas carentes de barrera ingenieril, y (ii) bajo un
enfoque de laboratorio; con muestras de un experimento de difusión con una arcilla natural
compactada hasta 0.5 m de altura en cuatro columnas independientes, cada una en contacto
durante cuatro años con un lixiviado distinto. En ambas actividades, se tomaron muestras de los
materiales a distintas profundidades y se midieron más de 30 parámetros: parámetros físico-
químicos (conductividad eléctrica, CE; potencial rédox, Eh; pH; carbono orgánico/inorgánico
total soluble, COTS/CITS; iones, alcalinidad…) y parámetros geológicos (cationes
intercambiables, capacidad de intercambio catiónico, CIC; humedad, h; superficie específica,
SSA; mineralogía, microfábrica, densidad). La importante cantidad de datos hizo necesario llevar
a cabo varios tratamientos estadísticos con el fin de (i) observar las correlaciones entre los
parámetros medidos y la atenuación de los contaminantes de los lixiviados (análisis de
componentes principales y rotación Varimax) y (ii) para saber qué efectos de los lixiviados en los
diferentes parámetros medidos en los materiales arcillosos son significativos (MANOVA, pruebas
entre-sujeto y pruebas múltiples).
A pesar de que los lixiviados han estado en contacto con los materiales naturales por largos
períodos de tiempo, los principales componentes solubles de los lixiviados fueron atenuados
(disminuyendo su concentración entre 90-100%) a una profundidad en la capa de arcilla de sólo
≤1.5 m desde el contacto de residuos/sustrato. Para cada sustrato natural, se definieron dos tipos
de valores: (i) la tasa de reducción para cada parámetro indicador de contaminación, por metro de
profundidad (Dm) y (ii) una capacidad de atenuación de flujo difusivo (Ac). El propósito fue
estudiar las diferencias entre los sustratos y comparar sus resultados como barrera geológica, en
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis | XXI
condiciones normalizadas de tiempo de exposición a los lixiviados y de cantidad de residuos
recibida por área.
Los materiales más adecuados son aquellos que tienen ≥47% de filosilicatos, caracterizados
por una proporción de illita/esmectita entre 1.8 y 5, con carbonatos y de alta densidad y SSA. Las
profundidades de atenuación observadas y las conductividades hidráulicas estimadas (K) en los
materiales naturales de este estudio, demostraron que la profundidad mínima y la K máxima de
una barrera geológica establecido por la Directiva 1999/31/CE (1999) son apropiadas para el
control de la contaminación de las principales especies solubles de los lixiviados. El NH4+ resultó
ser el parámetro más indicativo de la penetración de la contaminación de vertederos, reteniéndose
eficazmente a través de reacciones de intercambio. Esa capacidad de intercambio catiónico es
interesante de cara a la remediación ambiental de sitios contaminados. Asimismo, también se ha
discutido el importante papel que tienen la entrada de agua, los procesos de sorción, la
biodegradación, la capacidad tampón de pH, la naturaleza de los residuos, los tipos de arcillas, la
difusión y el equilibrio de precipitación-disolución, en los mecanismos de retardo en la migración
de contaminantes.
En general, se ha analizado en detalle la eficacia a largo plazo de varias barreras geológicas

debajo de vertederos de RU y se presentan datos fiables para el diseño de estrategias de atenuación
natural. Esta estrategia da lugar a una gestión de residuos más sostenible y más costo-efectiva en
relación con (i) los revestimientos de la instalación, (ii) sistemas de drenaje y recolección de gases
y (iii) el seguimiento post-clausura. Por ello, es una estrategia que conlleva una tecnología más
asequible para los países en vías de desarrollo, donde las enfermedades relacionadas con el agua
contaminada por residuos matan millones de personas al año, la mayoría niños.
PALABRAS CLAVE
Vertederos, arcillas, perfiles de parámetros en profundidad, atenuación natural.
XXII | Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis
ÍNDICE CONTENTS
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ÍNDICE DE FIGURAS TABLE OF FIGURES
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ÍNDICE DE TABLAS TABLE OF TABLES
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XXXII |
ÍNDICE DE FOTOS TABLE OF PHOTOS
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......................................................... 76
.............................................. 80

.................................. 81
....................................................................................... 83
............................................... 84
............................ 85
.................... 86
................................................................................... 87
.................................................................................. 96
................................................................................. 97
........................................................................... 98
.................................................................................. 99
................................................................................ 100
....................................................................... 101
....................................................................... 101
......................................... 102
........................................... 102
..................................................................... 103
..................................................................... 103
..................................................................... 104
....................................................................... 105
..................................................................... 105
..................................................................... 106
..................................................................... 107
..................................................................... 107
| XXXIII
....................................................................... 108
..................................................................... 108
.............................................................. 109
..................................................................... 109
............................................................................. 110
..................................................................... 111
........................................................ 112
....................................................................... 113
....................................................................... 113
....................................................................... 114
............................................................. 115
....................................................................... 115
.................................................................. 157
..................................................................... 173
........................................................................... 174
XXXIV |
ACRÓNIMOS Y ABREVIATURAS
X X
| XXXV
XXXVI |
ACRONYMS AND ABREVIATIONS
X X
| XXXVII
XXXVIII |
| 1
INTRODUCCIÓN
INTRODUCCIÓN
1.INTRODUCCIÓN
10 toneladas de RU
6
Vertedero Incineración Reciclaje

Compostaje Otros
2|
| 3
1.INTRODUCCIÓN
4|
1.1 Objetivos de la investigación
| 5
1.INTRODUCCIÓN
6|
1.2 Antecedentes y justificación
| 7
1.INTRODUCCIÓN
8|
Gas del vertedero

landfill gas
Vertedero
landfill
Lixiviado
leachate
Aguas subterráneas
groundwater
| 9
1.INTRODUCCIÓN
Verte-
dero
10 |
| 11
1.INTRODUCCIÓN
12 |
| 13
1.INTRODUCCIÓN
14 |
| 15
1.INTRODUCCIÓN
–
–
16 |
| 17
1.INTRODUCCIÓN
18 |

O2  H2O
NO3-  N2
MnO42-  Mn2+
Evolución de las concentraciones (sin escala)

Fe(OH)3  Fe2+
SO42-  S2-
CO2  CH4
Eh a pH 7: 400/500 300/200 200/100 -200/-300

400/300 -100/-200
Fig. 1.8 Secuencia y evolución de compuestos reducidos (arriba) y oxidados (abajo) al pasar de
condiciones aerobias a anaerobias. Potenciales rédox (Eh; mV) en los que ocurren las reacciones cuando
el pH del medio es 7.
Los siguientes vertederos más antiguos, se encuentran en la etapa anaerobia metanogénica o

básica. Durante esta etapa, bacterias metanogénicas terminan por convertir todos los ácidos
carboxílicos (fundamentalmente AGV) y subproductos producidos en la etapa acetogénica en
CH4, CO2, H2, agua y, se puede producir algo de NH3/NH4+ y H2S (1.9, 1.10). Los gases
principales son el CH4 y el CO2, correspondiendo al 60% y 40% del gas generado,
respectivamente. La transición de la etapa anterior acetogénica (última especie en reducirse: el
SO42-) a la etapa metanogénica ocurre a un potencial rédox menor, cuando comienza la reducción
del CO2, que pasa a CH4. Esta transición, se identifica por un aumento gradual en la generación
del gas CH4 al mismo tiempo que disminuye la generación de H2, CO2 y AGV.
AGV, CH3COOH(aq) + Oxidante  CH4(g) + CO2(g) + (NH3(g) + H2S(g)…) (1.9)
CO2(g) + 4H2(g) CH4(g) + 2H2O(l) (1.10)
El metano (que a diferencia del CO2 no se solubiliza y es muy volátil) se genera en grandes
cantidades, sobre todo al principio de la etapa (50-70%) por lo que algunos vertederos lo
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis | 19
1.INTRODUCCIÓN
20 |
| 21
1.INTRODUCCIÓN
22 |
| 23
1.INTRODUCCIÓN





24 |
| 25
1.INTRODUCCIÓN
26 |
·
·
·
·
| 27
1.INTRODUCCIÓN
28 |
| 29
1.INTRODUCCIÓN
30 |
| 31
1.INTRODUCCIÓN
32 |
| 33
1.INTRODUCCIÓN
34 |

Fig. 1.18 Estructura tipo clorita. Espaciado basal en condiciones originales (O), con etilenglicol (E) o
deshidratado (T).
Las figuras Fig. 1.14, Fig. 1.15, Fig. 1.16, Fig. 1.17 y Fig. 1.18 se modificaron del Geological
Society of London (2006).
Minerales de la arcilla 2:1 como ilitas, esmectitas y vermiculitas, tienen una carga
permanente negativa en sus capas (Tabla 1.10) debido a sustituciones de [Si4+]IV por [A13+]IV en la
capa T y/o de [Al3+, Fe3+]VI por [Mg2+, Fe2+]VI en la capa O (Brigatti et al., 2006). Este balance
negativo de cargas es neutralizado por cationes que se introducen en las posiciones interlaminares
de ilitas, esmectitas, vermiculitas. En el caso de las cloritas (2:1:1), la carga permanente negativa
se contrarresta por otras sustituciones de cationes en la capa octaédrica intermedia ([Mg2+]VI por
[Al3+, Fe3+]VI). Sin embargo, la caolinita (1:1) tiene idealmente carga neta neutra en sus capas,
aunque en la realidad, es difícil encontrar caolinitas puras que no tengan ninguna sustitución
iónica, sino que normalmente poseen una pequeña carga negativa, que se neutraliza por unos
pocos cationes interlaminares.
Si las arcillas están en contacto con agua, sus partículas se desagregan o dispersan. Algunos de
los cationes adsorbidos para neutralizar el déficit de carga de las sustituciones catiónicas, pasan así
a estar en contacto con la disolución. Éstos se hidratan y atraen a iones de carga negativa,
formando lo que se conoce como la doble capa difusa, en la que los cationes hidratados se
concentran más cuanto más cerca de la superficie arcillosa (Fig. 1.19).
Solución
Superficie arcilla
+ Catión
– Anión
Fig. 1.19 Doble capa difusa y distribución de los iones en disolución (van Olphen, 1977).
1.INTRODUCCIÓN
36 |
| 37
1.INTRODUCCIÓN
38 |
| 39
1.INTRODUCCIÓN
40 |
1.3 Marco legal
| 41
1.INTRODUCCIÓN
42 |
1.3 Marco legal
| 43
1.INTRODUCCIÓN
44 |
1.4 Estudios previos relacionados con la tesis
| 45
1.INTRODUCCIÓN
46 |
| 47
1.INTRODUCCIÓN
48 |

≤
| 49
1.INTRODUCCIÓN
50 |
| 51
MATERIALES Y MÉTODOS
2 MATERIALES Y MÉTODOS
MATERIALES Y MÉTODOS
52 |
2.1 Materiales
| 53
↑)
↑)
54 |
2.1 Materiales
| 55
↑)
↑)
56 |
2.1 Materiales
↑)
↑)
| 57
↑)
↑)
58 |
2.1 Materiales
↑)
↑)
| 59
60 |
2.1 Materiales

se ubica en las Margas de cuenca y se señala en la Fig. 2.7 con un aspa roja. Todos los materiales
descritos están afectados por fracturas de dirección NE – SO, que dan lugar a la fosa tectónica de
Bailén, que contacta al sur con la Depresión del Guadalquivir (Marín Señán et al., 2002).
Fig. 2.7 Mapa geológico del área de estudio y ubicación de la cantera de Bailén Cerámica
comercial Bailén S.A., concesión mineral nº 16018. MAGNA 50 hoja 905 – Linares (Cartografía
IGME).
En el 2005, se tomó una muestra de la arcilla de Bailén (A2) de 500 kg, almacenados en
bolsas de 20 kg (Foto 2.1). De los 500 kg, 100 kg se destinaron a ensayos y el resto como reserva.
Las muestras a analizar se secaron en horno rotatorio a 60 ºC y se molieron hasta pasar por un
tamiz de 5 mm (5·10-3 m). Su caracterización geotécnica y el contenido en óxidos poco ordenados
y carbono se resumen en la Tabla 2.3.

(g/cm3)
62 |
2.1 Materiales
~
~
~
| 63
Å
Å
θ Å
64 |
2.1 Materiales
↔ ∙
| 65
66 |
2.1 Materiales
| 67
68 |
2.2 Muestreo y preparación de muestras
| 69
70 |
| 71
a b c d
72 |
| 73
74 |
| 75
a b
c d e
76 |
2.3 Métodos analíticos
| 77
78 |
| 79
80 |
c1 c2
| 81
82 |
| 83
b
a
84 |
a
b
α λ
| 85
86 |
| 87
88 |
↔
| 89
RESULTADOS
3 RESULTADOS
↔
↔
RESULTADOS
90 |
3.1 Estudio de la barrera natural bajo vertederos reales
| 91
3 RESULTADOS
92 |
| 93
3 RESULTADOS
94 |
| 95
3 RESULTADOS
a) b)
96 |
a) b)
| 97
3 RESULTADOS
a) b)
c) d)
.
-
.
-
98 |
a) b)
c)
| 99
3 RESULTADOS
a) b)
c)
100 |
| 101
3 RESULTADOS
102 |
| 103
3 RESULTADOS
104 |
| 105
3 RESULTADOS
106 |
| 107
3 RESULTADOS
108 |
| 109
3 RESULTADOS
110 |
a
a
)
b
)
| 111
3 RESULTADOS
112 |
| 113
3 RESULTADOS
114 |
| 115
3 RESULTADOS
116 |
↔ ∙
↔ ∙
| 117
3 RESULTADOS
118 |
-
-
| 119
3 RESULTADOS
120 |
| 121
3 RESULTADOS
122 |
| 123
3 RESULTADOS
124 |
| 125
3 RESULTADOS
126 |

 
| 127
3 RESULTADOS
Z4V1 Z4V1
350 300
Z6V1 Z6V1
Z6V2 Z6V2
300 Z1V1 Z5V1
250
Z5V1
250
Eh (mV)
Eh (mV)
200
200
150
150
100 100
50 50
4 5 6 7 8 9 10 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
pH pH
128 |
300
Z4V1S1
Z4V1S2
250 Z4V1S3
MENOS PROFUNDAS
MAS PROFUNDAS
200
Eh (mV) 150
100
50
8.4 8.6 8.8 9.0 9.2 9.4 9.6 9.8
pH
350 Z1V1S1 Z5V1S1

220
Z1V1S2 Z5V1S2
325
MAS PROFUNDAS Z5V1S3
300 200
MENOS PROFUNDAS MAS PROFUNDAS
275 180
250
Eh (mV)
Eh (mV)
225 160
200 140
175
150 120
125 100
100
4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 6.5 7.0 7.5 8.0 8.5 9.0
pH pH
| 129
3 RESULTADOS
3000 2
Z4V1, r =0.19
2 900
2500 Z6V1, r =0.92
Z6V2,
2
r =0.83 800
2
2000 Z1V1, r =0.81 700
CITS (microg/g)
Z5V1, 2
r =0.41 600
CITS (microg/g)
1500 500
400
1000
300
500 200
100
0 0 Z6V2
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100
Alcalinidad (mmol/kg) Alcalinidad (mmol/kg)
130 |
| 131
3 RESULTADOS
132 |
| 133
3 RESULTADOS
µg
134 |
| 135
3 RESULTADOS
136 |
| 137
Transmission (%)
20
30
40
50
60
70
80
90
138 |
4250
4000
K
3750
3500
K, S, I
H20
3 RESULTADOS
3250
3000
Z6V1S1M01
2750
2500
2250
2000
1750
H20
1500 Carbonatos
-1
Wavenumber (cm )
1250
1000 Q, I, S, K
750
 K, S, I
Q, K F
500  S, I, K
250
0
Transmission (%)
20
30
40
50
60
70
80
90
4250
4000
K
3750
3500
K, S, I
H20
3250
3000
Z6V2S1M01
2750
2500 Carbonatos
2250
2000
1750 Carbonatos
H20
1500 Carbonatos
-1
Wavenumber (cm )
1250
1000 Q, I, S, K
750 Q, K
500  S, I, K
250
0
↔ ↔ ↔
| 139
3 RESULTADOS
140 |
| 141
3 RESULTADOS
142 |
| 143
3 RESULTADOS
144 |
| 145
3 RESULTADOS
146 |
| 147
3 RESULTADOS
148 |
| 149
3 RESULTADOS
150 |
| 151
3 RESULTADOS
152 |
| 153
3 RESULTADOS
8
7
6
Autovalor
5
4
3
2
1
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34
7
CP
154 |
| 155
3 RESULTADOS
156 |
3.2 Experimento de demostración sobre una barrera geológica añadida
| 157
3. RESULTADOS
158 |
| 159
3. RESULTADOS
θ
θ
θ
160 |
| 161
3. RESULTADOS
162 |
| 163
3. RESULTADOS
4000 A2L4M5.1-Air-dried
A2L1M5-Air-dried 500 A2L4M5.1-Etileneglycol
A2L1M5-Etileneglycol
3500 A2L1M5-Heating to 550‫؛‬C
A2L4M5.1-Heating to 550‫؛‬C
Intensity (arbitrary units)
-1.00
-, 1.36, 1.39
3000 400 -1.00
-1.71
2500 -1.00
-1.00 300
2000 -1.01
-1.47, 1.38
-1.01
-1.70
1500 -0.71
200
-0.71
1000
-0.71
500 -0.72 100
0
2 4 6 8 10 12 14 16 18 20 22 0
2 theta 2 4 6 8 10 12 14 16 18 20 22
2 theta
164 |
| 165
3. RESULTADOS
110
100
90
Transmission (%)
80
70
60
50
40
30 L4M01GQ
L4M02GQ
20 L4M03ANA
4500 4000 3500 3000 2500 2000 1500 1000 500 0
wavenumber (cm-1)
110 110
100 100
90 90
Transmission (%)
Transmission (%)
80 80
70 70
60 60
50 50
40 40
30 L4M01GQ 30 L4M01GQ
L4M02GQ L4M02GQ
20 L4M03ANA
20 L4M03ANA
4500 4000 3500 3000 2500 2000 1500 1000 5004500
0 4000 3500 3000 2500 2000 1500 1000 500 0
wavenumber (cm-1) wavenumber (cm-1)
166 |
110
100
90
Transmission (%)
80
70
60
50
40
30 L4M01GQ
L4M02GQ
20 L4M03ANA
4500 4000 3500 3000 2500 2000 1500 1000 500 0
wavenumber (cm-1)
110
100
90
Transmission (%)
80
70
60
50
40
30 L4M01GQ
L4M02GQ
20 L4M03ANA
4500 4000 3500 3000 2500 2000 1500 1000 500 0
wavenumber (cm-1)
| 167
3. RESULTADOS
168 |
a) b)
95 A2L3M01crust 105
A2L3M01
A2L3M02 100
90
A2L3M03 95
85
Transmission (%)
90
Transmission (%)
80 85
75 80
75
70
70
65 65
60 60
55 A2L4M01
55 A2L4M02
50 A2L4M03
50
4000
3960
3920
3880
3840
3800
3760
3720
3680
3640
3600
3560
3520
3480
3440
3400
3360
3320
4000
3960
3920
3880
3840
3800
3760
3720
3680
3640
3600
3560
3520
3480
3440
3400
3360
3320
Wavenumber (cm-1) Wavenumber (cm-1)
| 169
3. RESULTADOS
170 |
| 171
3. RESULTADOS
172 |
| 173
3. RESULTADOS
↔ ∙
↔ ∙
174 |
3
Dry density (g/cm )
1.50 1.55 1.60 1.65 1.70 1.75
0.0
A2L1
0.1 A2L3
A2L4
Depth (m)
0.2
0.3 A2L2
0.4
0.5
| 175
3. RESULTADOS
176 |
| 177
3. RESULTADOS
178 |
| 179
3. RESULTADOS
180 |
60 600
FTIR (altura, mm)
50 500
Shimadzu (COTS, µg/g)
40 400
30 300
20 200
10 100
0 0
N -- 1 2 3 -- 1 2 3
ILÉ M0 M0 M0 M0 M0 M0
BA 2 L3 2L3 2L3 2 L4 2L4 2L4
A2 A A A A A A
| 181
3. RESULTADOS
182 |
600 60
MO (mm altura pico) H (%)

500 50
400
40
300
30
COTS (µg/g)
200
100
C (%)
0
-100
N (%)
-200
-300 0
n
03
A2 01
A2 02
03
01 --
L3 t
A2 01
A2 02
L4 -
A2 rus
-
ilé
M
Ba
L3
L3
L4
L4
-
A2
A2
M
L3
A2
| 183
3. RESULTADOS
± ±
184 |
| 185
3. RESULTADOS
186 |
A2L2
2+
Ex_Mg (cmol(+)/kg) A2L3
A2L4
1 2 3 4 5 6 7 8 9
0.00
0.03
0.06
0.09
0.12
0.15
0.18
Depth (m)
0.21
0.24
0.27
0.30
0.33
0.36
0.39
0.42
0.45
0.48
0.51
0.54
0.57
| 187
3. RESULTADOS
188 |
| 189
3. RESULTADOS
190 |
| 191
3. RESULTADOS
.
.
192 |
220 200
A2L1 A2L2
A2L2 O2
200
A2L3
A2L4 195
180
160
190
Eh
Eh
3
4
140
O4
5 O3
120 185 2
1
100
180
7.6 7.8 8.0 8.2 8.4 8.6 8.8 9.0 7.6 7.7 7.8
pH pH
220 180
A2L3 A2L4
6
210 O4 170 O1
200 2 O6 O5 160
1
3
190 5 150
4
180 140
3 O2
Eh
Eh
170 2 5.1
130 1
160
120 5.2
150 O3 4
110
140 O2
100 O3
130
7.5 7.6 7.7 7.8 7.9 8.0 7.6 7.8 8.0 8.2 8.4 8.6 8.8 9.0
pH pH
| 193
3. RESULTADOS
194 |
| 195
3. RESULTADOS
α,
196 |
α >0.05
| 197
3. RESULTADOS
↑α <0.05
198 |
α)
| 199
3. RESULTADOS
200 |
201
DISCUSSION
4 DISCUSSION
DISCUSSION
202 |
4.1 Natural clayey barriers below real landfills
| 203
4 DISCUSSION
204 |
| 205
4 DISCUSSION
206 |
| 207
4 DISCUSSION
208 |
( )
| 209
4 DISCUSSION
210 |
| 211
4 DISCUSSION
212 |
Sheet silicates (%) Sheet silicates (%) Sheet silicates (%)
0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70 80
0.00 0.00 0.00
0.25 0.25 0.25
0.50 0.50 0.50
Depth (m)
Depth (m)
Depth (m)
0.75 0.75 0.75
1.00 1.00 1.00
1.25 1.25 1.25
1.50 1.50 1.50
1.75 Z5V1S1 1.75 Z5V1S2 1.75 Z5V1S3

0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
Calcite (%) Calcite (%) Calcite (%)
Dolomite (%) Dolomite (%) Dolomite (%)
| 213
4 DISCUSSION
100
90
SHEET SILICATES (%)

80
70
60
50
2
40 Z4V1, r = 0.88
2
30 Z6V1, r = 0.82
2
20 Z6V2, r = 0.76
2
10 Z1V1, r = 0.73
2
0 Z5V1, r = 0.15
0 20 40 60 80 100 120
2
Specific Surface (m /g)
 
214 |
| 215
4 DISCUSSION
3
Dry density (g/cm )
1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8
5
Depth (m from the top of the waste layer)
10 Z5V1
Z4V1
15 Z1V1
20
25
30 Z6V2
35
40
45 Z6V1
50
216 |
( )
𝜙 𝜙
| 217
4 DISCUSSION
≈
≈
218 |
| 219
4 DISCUSSION
220 |
– –
| 221
4 DISCUSSION
0.5
1
0.0
PC 1
2
6 5 10
4 9
13 7 12 35 7
89
10 68
11 4
-0.5 13
3
2 1
14 11
12 Z6V2
-0.5 0.0 0.5 1.0

PC 4
222 |
| 223
4 DISCUSSION
224 |
| 225
4 DISCUSSION
226 |
4.2 Demonstration experiment of the artificially established geological barrier
0.22 0.22
0.20 0.20
0.18 0.18
0.16 0.16
0.14 0.14
N (%)
N (%)
0.12 0.12
0.10 0.10
0.08 0.08
0.06 Linear fit: 0.06 Linear fit:
2 2
r =0.96299 r =0.82177
0.04 0.04
0 20 40 60 80 100 120 140 0 2 4 6 8
+ +
Sol_NH (mmol/kg)
4 Ex_NH (cmol+/kg)
4
| 227
4 DISCUSSION
228 |
| 229
4 DISCUSSION
230 |
| 231
4 DISCUSSION
 ↑
232 |

 
50
A2L1
45 A2L2
40 A2L3
A2L4
35 A2 original
30
% mass
25
20
15
10
5
0
Smectite Illite Chlorite
| 233
4 DISCUSSION
  


234 |
A2L2
SSA (m2/g) A2L3

A2L4
------ A2L1
16 18 20 22 24 26 28 30 32 34 36
0.0
Depth (m) 0.1
0.2
0.3
0.4
0.5
| 235
4 DISCUSSION
A2L1 Ratio A2L1 Ratio

0.0 0.5 1.0 1.5 2.0 2.5 0.00 0.02 0.04 0.06 0.08
0.00 0.00
0.05 0.05
0.10 0.10
0.15 0.15
0.20 0.20
0.25 0.25
Depth (m)
Depth (m)
0.30 0.30
0.35 0.35
0.40 0.40
0.45 0.45
0.50 0.50
Soluble cations Exchangeable cations
0.55 0.55
0 10 20 30 40 50 0.05 0.10 0.15 0.20 0.25 0.30
236 |
≈ ∙
∙ ≈
| 237
4 DISCUSSION
52 Linear fit A2L4

M3 2
r = 0.65
50 M5.1
Sheet silicates (%)
M2
48
M1 Shallowest sample: M01
M02
M02
46
M03
M5.2M
44 M5.1
M03
M4 M5.2
42 M4
M3
40 M01 M2
Deepest sample: M1
250 300 350 400 450 500 550 600 650 700
WSOC (microg/g)
238 |
| 239
240 |
4 DISCUSSION
Balance in L4
Quantity (µg/g or Leachate
-100
-50
0
50
100
150
200
Soil (Sandy loam)

mg/L) measured in:
Groundwater EC
Surface water W
SO
O C
rg
0
5
75
150
225
300
375
an N
ic H
C 4
(%
) N
a
Am pH
m K
on
C ia
hl C
or a
id
e M
Variables
g
Pb
C
Al l
C ka
r lin
ity
Fe
SO
C 4
d
C
0
u
100
200
300
-100
Zn
Exchangeable ions
Soluble ions Balance in clay:
| 241
4 DISCUSSION
242 |
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 


| 243
4 DISCUSSION
244 |
| 245
4 DISCUSSION
246 |
4.3 Comparison between the real landfill substrata and the Bailén demonstration experiment
| 247
4 DISCUSSION
248 |
| 249
4 DISCUSSION
250 |
≥ ·
| 251
4 DISCUSSION
 ≈
252 |
| 253
4 DISCUSSION
254 |
≥
.
255
CONCLUSIONS, REMARKS AND PERSPECTIVES
5 CONCLUSIONS, REMARKS AND PERSPECTIVES
CONCLUSIONS, REMARKS AND PERSPECTIVES
256 |
| 257
258 |
| 259
260 |
| 261
262 |
LIST OF REFERENCES
LIST OF REFERENCES
263
LIST OF REFERENCES
LIST OF REFERENCES
264 |
LIST OF REFERENCES
| 265
LIST OF REFERENCES
266 |
LIST OF REFERENCES
| 267
LIST OF REFERENCES
268 |
LIST OF REFERENCES
| 269
LIST OF REFERENCES
270 |
LIST OF REFERENCES
| 271
LIST OF REFERENCES
272 |
LIST OF REFERENCES
| 273
LIST OF REFERENCES
274 |
LIST OF REFERENCES
| 275
LIST OF REFERENCES
276 |
LIST OF REFERENCES
| 277
LIST OF REFERENCES
278 |
APPENDICES
APPENDICES
279
APPENDICES
280 |
SPANISH LEGISLATION. APPENDIX I
APPENDIX I. SPANISH LEGISLATION
- Ley 11/1997, de 24 de abril, de Envases y Residuos de Envases. BOE 99, de 25-4-1997.
- Orden de 27 de abril de 1998 por la que se establecen las cantidades individualizadas a

cobrar en concepto de depósito y el símbolo identificativo de los envases que se pongan en el
mercado a través del sistema de depósito, devolución y retorno regulado en la ley 11/1997, de
24 de abril, de Envases y Residuos de Envases. BOE 104, de 1-5-1998. Corrección de errores:
BOE 120, de 20-5-98.
- Real Decreto 782/1998, de 30 de Abril por el que se aprueba el Reglamento para el

desarrollo y ejecución de la ley 11/1997, de 24 de abril, de Envases y Residuos de Envases.
BOE 104, de 01-05-98.
- Resolución de 30 de septiembre de 1998, de la Dirección General de Tributos, relativa a la

aplicación del Impuesto sobre el Valor Añadido a determinadas operaciones efectuadas en el
marco de los sistemas integrados de gestión de envases usados y residuos de envases,
regulados en la Ley 11/1997, de 24 de abril, de Envases y Residuos de Envases, por las
entidades de gestión de los referidos sistemas y por otros agentes económicos. BOE 257, de
27-10-1998.
- Ley 50/1998, de 30 de diciembre, de Medidas Fiscales, Administrativas y de Orden Social

(modifica parcialmente la Ley 11/1997 de Envases y Residuos de Envases). BOE de 31-12-
1998
- Resolución de 13 de enero de 2000, de la Secretaría general de Medio Ambiente, por la

que se dispone la publicación del Acuerdo de Consejo de Ministros, de 7 de Enero de 2000,
por el que se aprueba el Plan Nacional de Residuos Urbanos. BOE 28, de 02-02-00.
- Orden de 22 de junio de 2001, por la que se establecen las condiciones para la no

aplicación a los envases de vidrio de los niveles de concentración de metales pesados
establecidos en el artículo 13 de la Ley 11/1997, de 24 de abril, de Envases y Residuos de
Envases. BOE de 19-06-01.
- Resolución de 3 de septiembre de 2003, de la Dirección General de Trabajo, por la que se

dispone la inscripción en el registro y publicación del Convenio Colectivo de Recuperación,
Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis A-1
APPENDIX I. SPANISH LEGISLATION
Transformación y Venta de Residuos y Desperdicios Sólidos. Documento pdf. BOE 228, de

23-09-03.
- Ley 10/1998 de 21 de abril, de Residuos. BOE 96, de 22-04-1998. Es la transposición de la

Directiva General de Residuos (91/156/CEE).
- Segundo Plan Nacional Integrado de Residuos, 2007–2015. Promueve un tratamiento y

gestión de residuos apropiados, disminuyendo su generación (28 240 470 t de RSU en 2007,
INE) y pretende que las administraciones públicas, consumidores y comerciantes asuman su
responsabilidad. Su antecesor, el I Plan Nacional Integrado de Residuos Urbanos 2000-2006,
surgió para trasponer la (CouncilDirective, 2008/98/EC) y desarrollar así la (Ley10/1998).
Dicho plan, recogía una serie de objetivos para el 2006 como son la reducción del 6% de la
generación de residuos, la recogida selectiva en todos los municipios de más de 1000
habitantes, la valorización de al menos el 50% de la materia orgánica por compostaje o la
clausura de los vertederos incontrolados. Fueron objetivos muy ambiciosos, teniendo en
cuenta que los residuos aumentaron un 29% de 1998 a 2008 y, consecuentemente, la cantidad
que fue tratada en vertederos (de 13 000 000 t a 16 000 000 t, más del 50% de los RSU)
(Ministerio de Agricultura, 2009).
A-2 Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis
EUROPEAN LEGISLATION. APPENDIX II
APPENDIX II. EUROPEAN LEGISLATION
- Directiva 1991/156/CEE del Consejo, de 18 de marzo de 1991, por la que se Modifica la

Directiva 75/442/CEE Relativa a los Residuos. DOCE 78/L, de 26-03-91.
- Directiva 1994/62/CE del Parlamento Europeo y del Consejo, de 20 de Diciembre de 1994,

relativa a los envases y residuos de envases. DOCE 365, de 31-12-94.
- Decisión 1997/129 de la Comisión, de 28 de Enero de 1997, por la que se establece el

sistema de identificación de materiales de envases, de conformidad con la Directiva 94/62/CE
del Parlamento Europeo y del Consejo, relativa a los envases y residuos de envases.
DOCE 50/L, de 20-02-97.
- Decisión 1997/138 de la Comisión, de 3 de Febrero de 1997, por la que se establecen los

modelos relativos al sistema de bases de datos, de conformidad con la Directiva 94/62/CE del
Parlamento Europeo y del Consejo, relativa a los envases y residuos de envases. DOCE 52/L,
de 22-02-97.
- Decisión 1999/42/CE de la Comisión, de 22 de Diciembre de 1998, por la que se

confirman medidas notificadas por Austria con arreglo al apartado 6 del artículo 6 de la
Directiva 94/62/CE del Parlamento Europeo y del Consejo relativa a los envases y residuos de
envases. DOCE 14/L, de 19-01-1999.
- Decisión 1999/177/CE de la Comisión, de 8 de Febrero de 1999, por la que se establecen

las condiciones para la no aplicación a las cajas de plástico y a las paletas de plástico de los
niveles de concentración de metales pesados fijados en la Directiva 94/62/CE relativa a los
envases y residuos de envases. DOCE 56/L, de 04-03-99.
- Directiva 1999/31/CE del Consejo, de 26 de abril de 1999, relativa al vertido de residuos.

DOCE L 182/1, de 16-07-1999.
- Decisión 2001/171/CE de la Comisión, de 19 de Febrero de 2001, por la que se establecen

las condiciones para la no aplicación a los envases de vidrio de los niveles de concentración
de metales pesados establecidos en la Directiva 94/62/CE relativa a los envases y residuos de
envases. DOCE 62/L, de 02-03-01.
APPENDIX II. EUROPEAN LEGISLATION
- Decisión 2003/33/CE del Consejo, de 19 de diciembre de 2002, por la que se establecen

los criterios y procedimientos de admisión de residuos en los vertederos con arreglo al
artículo 16 y al anexo II de la Directiva 1999/31/CE. DOCE L 11/27, de 16-01-2003. Esta
Decisión (CouncilDecision2003), desarrollo de la Directiva (CouncilDirective1999), clasifica
los vertederos de RSU dentro de los vertederos de residuos no peligrosos en la categoría B3
(vertederos para mezclas de residuos no peligrosos orgánicos biodegradables e inorgánicos).
DESCRIPTION OF LANDFILLS SAMPLES. APPENDIX III
APPENDIX III. DESCRIPTION OF LANDFILLS SAMPLES
CONTENTS Page
III.1. Z4V1 landfill description. A-7

Table III.1.1. Descriptions of samples from Z4V1S1 ................................................... A-7
Table III.1.2. Descriptions of samples from Z4V1S2 ................................................... A-9
Table III.1.3. Descriptions of samples from Z4V1S3 ................................................. A-11
III.2. Z6V1 landfill description. . A-13




III.1. Z4V1 landfill description.

Table III.1.1. Descriptions of samples from Z4V1S1
SAMPLES M Average depth and comments
0.01 m. Escasa consistencia. Arcillo-arenosa. Olor intenso a

M01
residuos.
M02 0.04 m. Similar a la anterior
0.13 m. Algo más arenosa. Escasa consistencia. Manchas

M05
moradas-negruzcas
0.18 m. Sección de forma irregular. Arcillo-arenosa. Manchas

M06
negruzcas extensas. Presencia de elementos gruesos
Salto en profundidad en la toma de las siguientes muestras
0.65 m. Parcialmente fragmentada. Arcillosa. Presencia de

M07
manchas grises. Presencia de elementos gruesos
1.15 m. Sección de forma irregular. Homogénea, algo más

M08
arenosa que la anterior
1.55 m. Arcillosa, compacta y homogénea. Algunas manchas

M09
grises.
2.25 m. Arcillosa. Homogénea. Mayor abundancia de manchas

M10
grises.
0.01 m. Color gris-rojizo. Arcilloso. Compacto. Olor moderado a

M01
residuos.
M04 0.09 m. Similar a la anterior, más arenosa.
0.13 m. Areno-arcillosa, con extensas manchas grisáceas y

M05
rojizas.
M06 0.17 m. Muestra fragmentada, irregular, similar a la anterior
0.19 m. Presencia escasa de manchas negras. Presencia de

M07
elementos gruesos (fragmentos de ladrillo)
0.75 m. Sección incompleta (8 cm) y de forma irregular en

M08 contacto con Salto en la toma de muestras. Presencia de material
rojizo. Escasos elementos gruesos alterados
1.35 m. Compacto. Homogéneo y arcilloso. Presencia de

M09
material rojizo
2.25 m. Presencia escasa de elementos gruesos. Homogénea,

M10
arenosa; escasa consistencia
4.15 m. Homogénea; más compacta que la anterior; areno-

M11
arcillosa
0.01 m. Fragmentado. Arcilloso. Color variegado (gris-rojizo).

M01
Olor ligero a residuos.
M02 0.04 m. Compacto y arcilloso. Presencia de manchas grises.
M05 0.13 m. Similar a la anterior, con escasas manchas grises
M07 0.63 m. Areno-arcillosa. Homogénea, de forma irregular.
M08 1.45 m. Arcillosa. Compacta. Presencia de manchas grises.
M09 2.55 m. Arcillosa, más seca que las anteriores.

0.01 m. Escasa consistencia. Presencia de residuos sin alterar.

M01 Olor intenso a residuos. De 41,600 a 41,560 m, capa constituida
fundamentalmente por basura. Muestra para lámina delgada
0.04 m. Abundancia de manchas negras. Olor moderado a

M02
residuos. Arcilloso y compacto
M05 0.11 m. Homogéneo. Escasa consistencia
0.16 m. Compacto. Predominio de tonos rojos con manchas

M06
grises
0.35 m. Sección divida en dos mitades transversales. Manchas

M08
grisáceas. Presencia de material oscuro en la zona superior.
0.42 m. Resto de 4 cm en contacto con parafinado. Muy

M09
compacto. Arcilloso
M10 0.95 m. Compacto, homogéneo y arcilloso.
M12 2.48 m. Homogéneo y arcilloso. Consistencia algo más débil
M13 3.55 m. Compacto, homogéneo y arcilloso. Manchas grises
M14 4.89 m. Compacto, homogéneo y arcilloso.
0.01 m. Material negruzco mayoritario. Escasa consistencia.

M01 Presencia de concentraciones blanquecinas. Olor moderado a
residuos.
0.04 m. Abundancia de manchas negras y elementos gruesos.

M02
Olor moderado a residuos. Arcilloso
0.06 m. Menor presencia de manchas negras. Olor moderado a

M03
residuos. Arcilloso
0.09 m. Similar a la anterior, con menor presencia de manchas

M04
negras.
M05 0.13 m. Similar a la anterior, sin manchas negras apreciables.
0.18 m. Muestra irregular, con predominio de material negruzco

M06 en la zona inferior de la muestra. Menor consistencia que las
anteriores
0.23 m. Compacto. Arcilloso. Presencia muy escasa de manchas

M07
negras.
0.68 m. Sección fragmentada (15 cm aproximados) y de forma

M08 irregular en contacto con Salto en la toma de muestras.
Arcilloso.
M09 1.15 m. Compacto y arcilloso
M10 2.32 m. Más arenoso que la anterior. Escasa consistencia

0.01 m. Escasa consistencia. Presencia de residuos sin alterar. Olor

M01
moderado a residuos.
0.04 m. Abundancia de manchas negras. Olor moderado a

M02
residuos. Arcilloso
0.25 m. Presencia escasa de manchas negras. Presencia de

M07
elementos gruesos
0.34 m. Sección incompleta (8 cm) y de forma irregular en

M08 contacto con Salto en la toma de muestras. Presencia de material
rojizo.
M09 1.00 m. Presencia de material rojizo
1.60 m. Presencia escasa de elementos gruesos. Homogénea,

M10
arenosa, escasa consistencia
3.30 m. Constituido en gran parte por gruesos (¿escombros?). Muy

M12
compacto
M13 4.70 m. Compacto, homogéneo y arcilloso
0.01 m. Color variegado (gris-rojizo). Aspecto irregular: zonas

M01
grises arenosas y rojizas arcillosas. No apreciables residuos.
0.04 m. Presencia de manchas negras, en disposición horizontal.

M02
Material areno-arcilloso
M03 0.06 m. Similar al anterior, con menos manchas negras.
0.09 m. Más arcilloso y homogéneo. No apreciables manchas

M04
negras.
M05 0.13 m. Color variegado gris-rojizo. Arcilloso
M06 0.18 m. Similar al anterior
M09 0.44 m. Similar al anterior, consistencia más débil
M10 1.05 m. Material arcilloso, homogéneo
M11 1.65 m. Más arenoso que el anterior, presencia de capas arcillosas
2.30 m. Arenoso, con capa arcillosa rojiza en la zona inferior de la

M12
sección
M13 3.47 m. Homogéneo. Arenoso
M14 4.70 m. Muy arenoso. Homogéneo y de escasa consistencia

0.01 m. Arcillosa. Presencia escasa de manchas negruzcas.

M01
Presencia de restos vegetales. Olor moderado

M02
0.06 m. Arcillosa. Presencia frecuente de manchas negruzcas.

M03
Restos vegetales. Olor moderado
0.09 m. Arcillosa. Escasas manchas negruzcas, poco

M04
contrastadas. Restos vegetales. Olor moderado
M05 0.13 m. Arcillosa. Escasos restos vegetales. Olor moderado
0.23 m. Arcillo-arenosa. Escasas manchas negruzcas. Restos

M06 vegetales. Olor moderado. Presencia de gravillas de arenisca,
amarillentas, alteradas
0.30 m. Arcillo-arenosa. Escasas manchas negruzcas. Olor

M07
moderado. Presencia de gravillas de arenisca, alteradas
0.38 m. Areno-arcillosa. Presencia de manchas grises y rojizas.

M08
Frecuentes gravillas alteradas, arenizadas
0.50 m. Areno-arcillosa. Presencia de manchas negruzcas, grises

M09
y rojizas. Frecuentes gravillas alteradas, arenizadas
1.10 m. Arcillo-arenosa. Presencia de manchas grises y rojizas.

M10
Presencia de gravillas de arenisca, alteradas.
1.25 m. Arcillo-arenosa. Presencia abundante de manchas

M11 negruzcas, grises y rojizas. Presencia de gravillas de arenisca,
alteradas.
1.35 m. Arcillo-arenosa. Presencia abundante de manchas

M12 negruzcas, grises y rojizas. Presencia de gravillas de arenisca,
alteradas.
1.65 m. Arcillosa. Presencia abundante de manchas grises y

M13
rojizas. Restos de raíces.

M14
rojizas.

M15
rojizas.

M01

M02

M03
0.09 m. Arcillo-arenosa. Presencia escasa de manchas negruzcas,

M04
poco contrastadas. Olor moderado

M05

M06
Olor moderado

M07
Olor moderado

M08
Presencia de restos vegetales. Olor ligero
M09 0.95 m. Arcillosa. Presencia escasa de manchas negruzcas.
1.07 m. Arcillosa. Presencia de gravillas de areniscas, gris-

M10
amarillentas, muy alteradas, en la parte inferior de la muestra
1.20 m. Arenisca compacta, poco alterada, ocre-parduzca, muy

M11
dura
2.52 m. Arenisca compacta, grisácea, poco alterada, muy dura;

M12
presencia de manchas negruzcas
3.63 m. Arenisca compacta, grisácea, poco alterada, muy dura.

M13
Presencia de manchas rojizas.

0.03 m. Olor fuerte a residuos de industria. Al cortar huele

más a residuos domésticos. Capa externa color marrón pero
M01
dentro tiene color negro. Se deshace en trozos grandes y
pequeños.
M02 0.08 m. Igual que la muestra 01, pero con menos humedad
0.12 m. No tiene de color negro el interior. Presenta una

M03
zona con un color verde blanquecino. Es más seca.
0.17 m. Al partirla tiene un bandeado de tono claro-oscuro-

M04
claro-oscuro. Fuerte olor a amoníaco
0.85 m. Muestra arenosa. Color uniforme de tonalidad

M05
verdosa.
1.75 m. Muestra arenosa. Color uniforme de tonalidad

M06
marrón.
0.02 m. La parte más profunda es más clara. Posee una cáscara

M01
marrón oscuro. Fuerte olor.
0.05 m. Similar a la anterior, pero color más claro en el interior y

M02
la cáscara más oscura.
M03 0.08 m. Similar a la muestra 02
M04 0.12 m. Similar a la muestra anterior.
0.20 m. Corteza más clara. Se observan alternancias de zonas

M05 oscuras, claras y más amarillentas en el interior de la muestra. En
general, predominio del color grisáceo.
M06 0.30 m. Muy similar a la muestra 05
0.68 m. Color marrón, muy oscuro. Muestra altamente húmeda.

M07 Se pega a las manos. Al partirla, se ven colores negros. Textura
exfoliante, gran cantidad de arenas grandes.
0.02 m. Contiene restos de basura (trozo de plástico, trozo de

cristal, un cartón gordo.). Se pega a las manos, pero al cortar
M01 se fractura (en su interior no tiene textura plástica). Color
marrón y por dentro marrón mucho más oscuro, con zonas
negras. Olor fuerte a basura. Muestra muy húmedo.
0.05 m. Similar a la muestra anterior. Restos de basura

M02
encontrados: trozos de tejido.
0.08 m. Similar que las anteriores, pero en el interior tiene un

M03 color menos oscuro. Aparecen más piedras de pequeño
tamaño.
0.11 m. Similar a la muestra 03, pero de color más negro, y

M04
con menos piedras.
0.17 m. Muestra mucho más pesada que las anteriores. Color

marrón y mucho más claro que las muestras previas. También
M05 tiene menos humedad. Se ven mayoritariamente manchas
amarillas-cobrizas, y en menor abundancia manchas blancas,
que son más pequeñas.
0.27 m. Al igual que la muestra 05 es mucho más pesada que

la 04, 03, 02, 01. Color marrón y claro. También tiene menos
humedad. Se ven manchas amarillas-cobrizas de mayor
M06
extensión que la muestra 05. Manchas blancas más pequeñas,
pero más abundantes que en M05. La segunda mitad de la
parte más profunda, presenta mayor resistencia a la rotura.
0.57 m. Muestra de color marrón oscuro, con tonos verdosos.

M07 Alta humedad. Las muestras se rompían en pedazos, ésta se
desmenuza en arena. Se encuentra un trozo de tejido.
1.05 m. Es algo menos húmeda que la muestra anterior, pero

todavía tiene una humedad significativa. También es algo
M08
menos oscura, con color marrón. Muestra una gran resistencia
a ser cortada.
1.70 m. Similar a la anterior, pero con muchas piedras y

M09
mucho más fácil de cortar (menos compactada)
APPENDIX IV. PARAMETERS DATA MEASURED IN THE LANDFILLS SUBSTRATA
IV.1 Z4V1 landfill ......................................................................................................................................................................................................................... A-35

Table IV.1.1 Depths from the surface, thicknesses and depths from the landfill base of the samples from Z4V1 landfill ........................................... A-35
Table IV.1.2 pH, redox potential, electrical conductivity, water soluble organic/inorganic carbon, moisture of Z4V1 samples ................................. A-35
Table IV.1.3 Soluble ions (mmol/kg) in aqueous extracts of Z4V1 samples ................................................................................................................. A-36
Table IV.1.4 Heavy metals (µg/g) and Fe (mg/g) of Z4V1 samples.............................................................................................................................. A-36
Table IV.1.5 Exchangeable cations and cationic-exchange capacities [cmol(+)/kg] of Z4V1 samples ........................................................................ A-37
Table IV.1.6 Semi-quantitative average mineralogical composition (mass %, DRX) and specific surface area (m2/g) of Z4V1 samples ................... A-38
Table IV.1.7 Semi-quantitative sheet silicates composition (mass %, DRX) from selected Z4V1 samples ................................................................. A-38
Fig. IV.1.1 X-ray powder-diffraction patterns (a.u: arbitrary units) of Z4V1S1. .......................................................................................................... A-39
Fig. IV.1.2 X-ray diffraction patterns (a.u: arbitrary units) of oriented slides of Z4V1S1M07 ..................................................................................... A-39
IV.2. Z6V1 landfill........................................................................................................................................................................................................................ A-41
Table IV.2.6 Semi-quantitative mineralogical composition (mass %, DRX) and specific surface area (m2/g) of Z6V1 samples ................................ A-44
A-31 Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis LANDFILLS DATA. APPENDIX IV
IV.3 Z6V2 landfill ......................................................................................................................................................................................................................... A-47
IV.4. Z1V1 landfill........................................................................................................................................................................................................................ A-53
IV.5 Z5V1 landfill......................................................................................................................................................................................................................... A-59
Table IV.5.4 Heavy metals (µg/g) and iron (mg/g) of Z5V1 samples ........................................................................................................................... A-60
Table IV.5.6 Semi-quantitative average mineralogical composition (mass %, DRX) and specific surface area (m2/g) of Z5V1 samples ................... A-62
Conversion to SI units: equivalence

Lengh: 1 cm 10-2 m
equivalence
Electrical conductivity: 1 mS/cm 102 mS/m
IV.1. Z4V1 landfill
Table IV.1.1 Depths from the surface, thicknesses and depths from the landfill base of the samples from Z4V1 landfill
Z4V1S1 Z4V1S2 Z4V1S3

Minimum & Minimum & Minimum &
Average Average Average
maximum Thickness maximum Thickness maximum Thickness
Sample depthb Sample depthb Sample depthb
depthsa (cm) depths a
(cm) depthsa (cm)
(m) (cm) (m)
(m) (m) (m)
M01 16.500-16.525 2.5 0.01 M01 14.00-14.025 2.5 0.01 M01 10.800-10.825 2.5 0.01
M02 16.525-16.55 2.5 0.04 M02 14.025-14.05 2.5 0.04 M02 10.825-10.85 2.5 0.04
M03 16.55-16.575 2.5 0.06 M03 14.05-14.075 2.5 0.06 M03 10.85-10.875 2.5 0.06
M04 16.575-16.60 2.5 0.09 M04 14.075-14.10 2.5 0.09 M04 10.875-10.90 2.5 0.09
M05 16.60-16.65 5.0 0.13 M05 14.10-14.15 5.0 0.13 M05 10.90-10.95 5.0 0.13
M06 16.65-16.70 5.0 0.18 M06 14.15-14.18 3.0 0.17 M06 10.95-11.00 5.0 0.18
M07 17.10-17.20 10.0 0.65 M07 14.18-14.20 2.0 0.19 M07 11.38-11.48 10.0 0.63
M08 17.60-17.70 10.0 1.15 M08 14.70-14.80 10.0 0.75 M08 12.20-12.30 10.0 1.45
M09 18.00-18.10 10.0 1.55 M09 15.30-15.40 10.0 1.35 M09 13.30-13.40 10.0 2.55
M10 18.70-18.80 10.0 2.25 M10 16.20-16.30 10.0 2.25
M11 18.10-18.20 10.0 4.15
a
Depths measured from the surface (i.e., including the waste), b Average depth measured from the waste bottom.
Table IV.1.2 pH, redox potential (Eh: mv), electrical conductivity (EC: mS/cm), water soluble organic/inorganic carbon (WSOC/WSIC: µg/g), moisture (h: %) of
Z4V1 samples
Sample
pH Eh EC WSOC WSIC h pH Eh EC WSOC WSIC h pH Eh EC WSOC WSIC h
M01 8.6 162 11.300 149 1202 29.56 8.5 87 7.240 509 197 17.03 8.4 286 0.489 82 114 18.54
M02 8.7 154 11.220 153 1111 25.91 8.6 83 6.520 400 192 16.11 8.8 232 0.191 82 102 18.55
M03 8.6 147 11.220 516 615 26.40 8.6 73 7.100 428 190 15.17 8.7 216 0.144 55 90 18.27
M04 8.6 142 10.700 143 1150 23.10 8.6 74 6.420 365 171 15.94 8.8 192 0.149 44 89 19.76
M05 8.8 137 15.970 101 1649 39.60 8.7 113 6.420 319 184 18.64 8.7 178 0.157 45 85 18.91
M06 8.7 120 10.470 134 2554 24.17 8.7 102 5.610 294 171 16.33 8.8 166 0.149 50 92 16.80
M07 8.9 153 10.000 193 397 29.50 8.5 113 4.190 114 92 15.81 8.7 216 0.144 45 88 13.71
M08 8.7 167 6.100 133 183 24.54 9.2 204 0.488 102 136 21.72 8.8 192 0.149 46 94 15.55
M09 9.2 141 0.807 125 141 16.09 9.1 261 0.647 98 129 21.04 8.7 178 0.157 101 129 10.36
M10 9.2 159 0.815 143 195 18.61 9.6 118 0.369 96 98 16.11
M11 9.7 111 0.338 109 97 11.56
Table IV.1.3 Soluble ions (mmol/kg) in aqueous extracts of Z4V1 samples

Soluble cations Soluble anions Soluble cations Soluble anionsa Soluble cations Soluble anions
Sample
NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk SO42- F- NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk F- NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk SO42- F-
M01 6.81 414 7.54 9.71 8.89 568 22.26 9.94 4.51 9.67 217.46 6.43 6.52 2.74 448.0 33.30 2.16 0.36 4.75 1.87 15.62 7.51 2.67 9.00 12.99 0.37
M02 7.18 364 6.51 6.77 5.65 539 21.76 9.46 4.24 8.22 246.58 6.70 7.38 6.34 446.0 30.65 1.99 n.d. 3.58 0.37 7.48 3.63 1.78 6.83 1.97 0.42
M03 7.51 399 6.79 8.25 6.78 548 18.17 9.83 4.21 7.73 197.82 5.43 7.67 7.73 426.0 28.21 1.86 n.d. 3.02 0.31 5.88 3.11 1.10 5.99 0.16 0.40
M04 7.03 381 5.83 6.00 4.32 504 18.36 9.36 4.18 8.28 204.47 5.47 7.46 34.89 302.0 26.06 1.15 n.d. 3.22 0.32 4.45 3.21 1.27 5.73 0.22 0.37
M05 14.32 630 6.67 23.89 31.75 806 36.01 11.40 5.31 11.69 181.06 4.80 5.28 2.03 285.0 27.26 1.00 n.d. 3.09 0.38 6.57 3.12 1.67 5.95 0.21 0.34
M06 7.51 372 4.62 6.67 6.96 509 28.16 15.80 4.09 10.06 271.96 5.97 9.81 5.81 282.0 32.66 0.91 n.d. 2.71 0.49 4.97 3.00 1.40 7.55 0.49 0.30
M07 1.66 223 2.82 4.41 3.03 352 26.31 17.40 n.d. 3.58 113.03 2.36 7.19 5.15 192.0 12.42 0.21 n.d. 4.74 1.17 5.20 2.39 1.11 8.79 0.55 0.16
M08 1.28 156 1.21 6.57 4.91 198 13.69 7.54 0.24 n.d. 18.44 0.72 3.79 2.07 14.7 16.64 0.49 n.d. 2.61 0.29 5.90 2.52 0.89 8.36 n.d. 0.39
M09 0.40 23.8 0.66 2.03 2.61 44.3 13.65 1.95 0.25 n.d. 19.47 0.65 4.90 3.06 8.74 16.28 0.46 n.d. 9.96 1.44 4.02 0.44 1.09 9.86 0.48 0.35
M10 0.40 27.9 1.07 2.11 1.90 16.9 8.88 0.71 0.28 n.d. 12.97 0.48 3.83 2.26 4.23 10.97 0.22
M11 n.d. 8.54 1.08 4.74 2.74 3.38 9.66 0.10
Alk: alkalinity, n.d.: no detected.a SO42- concentrations no detected in S2.
Table IV.1.4 Heavy metals (µg/g) and Fe (mg/g) of Z4V1 samples

Sample
Zn Cd Pb Cr Cu Fe Zn Cd Pb Cr Cu Fe Zn Cd Pb Cr Cu Fe
M01 110.6 0.123 45.6 312.9 120.5 38.5 115.6 0.113 36.5 90.7 36.6 27.0 132.7 0.454 33.9 78.9 50.4 42.1
M02 111.7 0.147 36.0 211.2 47.0 38.6 108.8 0.071 30.2 58.7 28.9 27.1 137.4 0.438 28.7 66.8 40.5 42.2
M03 104.5 0.134 41.5 243.9 36.9 33.6 130.3 0.068 30.0 66.0 32.5 28.4 132.7 0.435 27.4 58.1 39.4 41.7
M04 103.1 0.088 32.0 176.0 35.6 36.0 101.3 0.062 24.7 55.4 26.9 25.8 128.1 0.436 24.7 49.1 39.4 41.0
M05 180.6 0.300 52.8 163.0 168.2 26.4 89.0 0.035 20.2 67.2 25.3 27.5 120.1 0.435 21.8 56.3 35.7 38.7
M06 98.5 0 0.121 34.6 259.1 50.2 33.1 100.0 0.041 20.9 72.1 31.1 27.3 115.9 0.510 22.3 51.1 38.2 35.9
M07 127.2 0.196 41.5 358.2 35.2 46.1 90.4 0.031 20.6 64.2 26.1 30.0 72.4 0.351 11.7 36.1 30.4 28.3
M08 123.0 0.086 35.3 67.5 34.4 46.9 140.4 0.044 32.6 122. 45.8 47.1 110.9 0.302 14.2 59.6 38.1 43.1
M09 125.0 0.113 36.0 77.5 35.5 46.6 142.8 0.094 28.9 123. 49.7 46.8 118.7 0.390 22.8 47.7 43.1 44.6
M10 135.1 0.158 42.4 99.3 41.9 50.7 103.2 0.134 23.6 74.3 27.8 32.8
M11 69.2 0.032 13.7 43.4 19.2 25.3
Table IV.1.5 Exchangeable cations and cationic-exchange capacities [cmol(+)/kg] of Z4V1 samples

Sample Exchangeable cations CEC Exchangeable cations CEC Exchangeable cations CEC
NH4+ Na+ K+ Ca2+ Mg2+ Σ NH4+ Na+ K+ Ca2+ Mg2+ Σ NH4+ Na+ K+ Ca2+ Mg2+ Σ
M01 0.38 6.81 1.08 37.88 8.88 55.03 18.8 0.59 3.32 0.59 29.67 4.81 38.98 8.7 n.d. 0.1 0.48 42.32 10.72 53.62 19.5
M02 0.36 7.45 1.17 35.9 9.12 54 14.8 0.51 2.89 0.53 28.54 4.77 37.24 9.7 n.d. 0.1 0.28 42.05 12.94 55.37 26.8
M03 0.58 7.13 1.09 35.56 8.34 52.7 13.7 0.48 2.58 0.47 28.21 4.95 36.69 8.0 n.d. 0.2 0.16 41.9 13.12 55.38 26.0
M04 0.57 6.93 1.29 31.08 7.52 47.39 20.5 0.53 2.42 0.5 27.38 4.98 35.81 8.2 n.d. 0.16 0.13 40.44 10.48 51.21 23.9
M05 0.76 6.49 0.66 37.53 16.17 61.61 22.2 0.72 3.15 0.51 29.19 5.16 38.73 7.4 n.d. 0.21 0.29 37.3 9.01 46.81 19.4
M06 0.66 5.79 1.06 35.5 14.61 57.62 18.4 0.55 2.28 0.43 51.07 3.23 57.56 10.3 n.d. 0.18 0.23 30.28 11.64 42.33 18.3
M07 0.41 7.84 0.79 51.81 10.82 71.67 21.7 0.23 1.63 0.32 27.76 6.4 36.34 9.6 n.d. 0.09 0.17 37.57 4.9 42.73 6.6
M08 0.24 3.65 0.29 30.22 13.28 47.68 25.6 n.d. 0.91 0.38 57.8 23 82.09 23.8 n.d. 0.12 0.17 52.74 14.24 67.27 21.3
M09 0.1 1.41 0.32 44.56 19.21 65.6 23.0 n.d. 0.71 0.3 56.66 20.24 77.91 22.6 n.d. 0.43 0.31 45.19 14.25 60.18 12.7
M10 0.13 1.98 0.46 45.17 19.24 66.98 24.6 n.d. 0.18 0.3 43.88 11.55 55.91 10.7
M11 n.d. 0.09 0.24 39.68 5.04 45.05 4.9
Σ: sum of exchangeable cations, CEC: cationic-exchange capacity, n.d.: no detected.
Table IV.1.6 Semi-quantitative average mineralogical composition (mass %, DRX) and specific surface area (m2/g) of Z4V1 samples
Z4V1S1 Z4V1S2a Z4V1S3

Sample Sheet Feldspars e Sheet Feldspars e Sheet Feldspars
Quartz Calcite Dolomite S Quartz Calcite S Quartz Calcite Dolomite Se
silicates Na K silicates Na K silicates Na K
M01 47 21 2 2 28 0 16 30 39 3 4 24 6 56 21 2 1 19 2 28
M02 50 19 2 1 27 0 20 28 50 2 5 16 7 59 20 2 1 15 3 33
M03 55 17 2 1 25 1 18 27 52 4 4 13 10 65 16 2 1 14 2 32
M04 53 17 1 1 27 1 21 28 44 4 11 14 8 68 15 2 1 13 2 27
M05 41 17 3 1 38 0 18 26 50 8 4 13 11 51 21 3 1 23 2 22
M06 42 24 2 1 31 1 19 27 49 4 4 16 10 38 29 2 2 27 2 20
M07 62 18 2 1 13 4 29 26 49 4 3 17 9 22 49 3 4 19 3 9
M08 76 12 1 1 8 3 29 75 13 2 1 9 37 60 22 1 3 12 2 30
M09 60 19 2 1 14 5 31 63 20 2 1 14 31 51 26 3 1 15 4 26
M10 74 9 2 1 10 4 39 39 35 3 1 22 15
M11 22 52 4 2 21 7
a
Dolomite was not detected in borehole S2. Se: specific surface area.
Table IV.1.7 Semi-quantitative sheet silicates composition (mass %, DRX) from selected Z4V1 samples

Sample
Illite Smectite Chlorite Illite Smectite Chlorite Illite Smectite Chlorite
M01 26 13 8 17 8 5 15 11 56
M02 26 15 10 15 8 5 19 8 59
M03 28 15 11 14 8 5 23 10 65
M04 31 14 9 15 8 5 24 11 68
M05 24 10 7 15 6 5 14 8 51
M06 24 11 7 12 6 38
M07 31 21 10 14 8 5 4 6 22
M08 35 30 11 35 27 12 20 9 60
M09 30 21 9 31 22 10 16 9 51
M10 39 22 12 20 12 6
M11 12 6 4
Z4 / V1 / S1
Z4 / V1 / S1
Intensity (a.u.)
(u.a.)
Intensidad (u.a.)
M06
Intensidad
Intensity (a.u.)
M05
M04
M03
M02
M01
2θ (º) 2θ (º)
Fig. IV.1.1 X-ray powder-diffraction patterns (a.u: arbitrary units) of Z4V1S1.
Fig. IV.1.2 X-ray diffraction patterns (a.u: arbitrary units) of oriented

slides of Z4V1S1M07
Clays were studied in three oriented aggregates using standard methods
involving: drying at room temperature, solvation with glycerol (0.1:2 clay-to-
water+glycerol ratio) and heating at 550ºC for 24 h (0.1:2 clay-to-water)
(Moore and Reynolds, 1997).
Z4 / V1 / S2
Z4 / V1 / S2
Intensity (a.u.)
(u.a.)
(a.u.)(u.a.)
Intensidad
M09
Intensidad
M07
Intensity
M05
M03
M01
2θ (º) 2θ (º)

slides of Z4V1S2M07
IV.2. Z6V1 landfill
Z6V1S1 Z6V1S2
Minimum & maximum depthsa Thickness Average depthb Minimum & maximum depthsa Thickness Average depthb
Sample Sample
(m) (cm) (m) (m) (cm) (m)
M01 41.60-41.625 2.5 0.01 M01 45.25-45.275 2.5 0.01
M02 41.625-41.65 2.5 0.04 M02 45.275-45.30 2.5 0.04
M03 41.65-41.675 2.5 0.06 M03 45.30-45.325 2.5 0.06
M04 41.675-41.700 2.5 0.09 M04 45.325-45.35 2.5 0.09
M05 41.70-41.725 2.5 0.11 M05 45.35-45.40 5.0 0.13
M06 41.750-41.775 2.5 0.16 M06 45.40-45.45 5.0 0.18
M07 41.80-41.90 10 0.25 M07 45.45-45.50 5.0 0.23
M08 41.90-42.00 10 0.35 M08 45.85-46.00 15.0 0.68
M09 42.00-42.04 4 0.42 M09 46.35-46.45 10.0 1.15
M10 42.50-42.60 10.0 0.95 M10 47.52-47.62 10.0 2.32
M11 43.24-43.34 10.0 1.69 M11 48.15-48.25 10.0 2.95
M12 44.02-44.14 12.0 2.48 M12 48.69-48.79 10.0 3.49
M13 45.10-45.20 10.0 3.55
M14 46.43-46.55 12 4.89
a
Z6V1 samples
Z6V1S1 Z6V1S2
Sample
pH Eh EC WSOC WSIC h pH Eh EC WSOC WSIC h
M01 8.6 130 2.500 753 410 24.23 8.9 136 2.480 391 394 21.76
M02 9.1 114 1.140 401 270 19.83 9.1 126 1.810 475 366 22.67
M03 9.1 122 1.010 282 262 21.95 9.0 132 1.710 344 325 23.55
M04 9.1 130 1.160 246 277 22.28 9.1 136 1.580 345 279 24.01
M05 9.1 136 1.250 170 268 19.62 9.0 143 1.440 335 221 21.04
M06 9.0 166 1.350 192 276 21.04 9.1 126 1.730 535 344 21.94
M07 8.9 169 1.130 87 196 21.93 9.0 142 1.190 166 157 19.10
M08 8.8 176 1.140 57 161 20.44 8.7 153 1.270 63 101 —
M09 8.9 175 1.110 81 143 20.94 8.8 164 1.310 74 115 21.08
M10 9.0 181 1.060 37 45 22.92 8.9 152 1.020 71 74 19.95
M11 9.0 165 1.020 98 84 21.60 8.9 165 1.160 93 98 25.79
M12 8.9 149 1.250 249 149 23.98 8.8 179 1.070 33 45 26.10
M13 8.8 151 1.400 166 176 26.00
M14 8.8 155 0.910 58 45 17.35
Z6V1S1 Z6V1S2
Soluble cations Soluble anions Soluble cations Soluble anions
Sample
NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk SO42- F- NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk SO42- F-
M01 72.19 45.36 16.51 16.59 8.05 18.60 80.10 4.58 n.d. 89.42 47.47 15.44 3.27 0.97 18.00 96.72 6.61 n.d.
M02 42.87 31.10 7.64 3.29 1.76 13.40 53.94 2.66 n.d. 65.96 26.67 11.68 61.20 0.92 19.60 79.82 4.27 n.d.
M03 36.58 32.57 6.54 2.83 2.81 12.40 53.04 2.78 n.d. 56.41 41.27 13.69 2.73 0.90 18.90 69.11 4.34 n.d.
M04 33.44 31.35 7.05 2.64 2.81 11.50 54.24 3.10 n.d. 51.27 32.18 10.67 3.40 1.19 18.30 56.50 4.06 n.d.
M05 22.48 27.79 5.75 3.41 3.87 9.80 46.23 5.08 n.d. 37.51 20.81 6.97 1.78 0.62 18.60 49.25 3.87 n.d.
M06 21.31 30.83 6.78 4.31 4.81 10.50 42.19 6.08 n.d. 52.19 40.36 13.15 2.68 1.15 19.30 66.65 3.51 n.d.
M07 11.90 20.79 3.23 3.60 5.04 7.90 26.17 6.97 n.d. 31.19 21.54 6.44 1.36 0.82 14.40 46.30 3.23 n.d.
M08 11.07 22.96 4.54 8.36 6.64 6.80 19.13 8.72 n.d. 6.61 14.11 2.84 4.02 3.43 11.20 13.85 9.52 n.d.
M09 5.16 13.10 4.13 25.88 6.46 6.90 21.96 8.94 n.d. 4.72 20.71 2.71 7.87 4.83 9.67 15.12 8.67 n.d.
M10 n.d. 5.87 2.01 21.65 5.98 2.90 8.53 11.40 n.d. 4.84 11.69 1.91 9.10 4.45 5.47 11.87 10.80 n.d.
M11 2.60 8.74 2.13 18.07 6.38 4.90 12.24 9.12 n.d. 5.80 17.63 2.66 10.63 5.25 6.40 13.44 9.05 n.d.
M12 11.47 9.17 2.75 46.44 7.49 7.50 20.84 10.90 n.d. 0.28 27.36 1.28 8.90 5.89 4.82 5.36 12.00 n.d.
M13 3.87 15.90 4.63 8.97 6.82 4.90 17.49 13.80 n.d.
M14 n.d. 14.80 1.19 4.88 4.40 1.40 4.22 9.80 n.d.
Alk: alkalinity, n.d.: no detected.
Z6V1S1 Z6V1S2
Sample
Zn Cd Pb Cr Cu Fe Zn Cd Pb Cr Cu Fe
M01 97.2 0.118 113.2 77.4 29.9 45.8 82.8 0.063 87.0 52.3 26.7 40.5
M02 89.1 0.145 79.8 72.3 24.9 45.1 83.9 0.139 137.5 45.3 33.7 40.7
M03 91.1 0.230 87.9 74.5 24.8 47.3 79.6 0.091 129.9 41.5 32.9 35.6
M04 93.9 0.109 79.7 64.7 26.7 46.1 77.8 0.075 106.3 34.9 32.2 35.3
M05 110.8 0.264 71.8 63.8 33.8 50.0 68.6 0.062 101.6 35.3 32.8 34.7
M06 112.3 0.335 82.1 60.2 34.7 48.0 79.7 0.125 119.8 37.6 37.8 34.2
M07 81.5 0.114 46.1 57.2 32.5 36.3 56.2 0.128 68.1 39.5 23.3 30.1
M08 77.5 0.264 57.2 79.2 34.7 39.3 120.8 0.065 133.6 61.3 41.4 48.3
M09 76.1 0.085 45.6 61.3 31.2 37.7 63.1 0.029 53.2 62.2 31.5 29.2
M10 70.2 0.082 33.0 50.7 30.3 33.1 92.6 0.098 86.6 42.3 28.6 39.3
M11 57.6 0.104 22.1 37.4 28.3 28.8 63.6 0.030 69.3 52.7 38.9 34.0
M12 68.1 0.079 23.5 49.0 31.4 32.2 120.8 0.065 133.6 41.6 27.1 48.3
M13 119.0 0.537 62.7 76.6 35.2 51.8
M14 81.5 0.189 47.5 61.5 38.8 41.4
Z6V1S1 Z6V1S2
Sample Exchangeable cations Exchangeable cations
CEC CEC
NH4+ Na+ K+ Ca2+ Mg2+ Σ NH4+ Na+ K+ Ca2+ Mg2+ Σ
M01 3.66 1.16 1.3 19.58 12.15 37.85 11.2 6.46 1.35 2.12 45.78 7.56 63.27 13.5
M02 2.98 1.31 1.16 10.09 11.97 27.51 11.2 5.28 1.29 1.62 25.32 7.66 41.17 10.4
M03 2.71 1.29 1.13 10.5 15.65 31.28 10.0 4.16 1.13 0.94 21.43 8.5 36.16 13.9
M04 2.71 1.48 1.09 15.35 11.15 31.78 11.2 2.25 0.95 0.9 20.48 8.92 33.5 11.0
M05 2.24 1.07 0.99 12.42 14.35 31.07 14.4 2.87 0.95 0.68 8.65 6.71 19.86 5.8
M06 2.32 1.37 1.13 20.02 17.04 41.88 12.7 3.71 0.88 0.69 20.87 6.81 32.96 11.3
M07 0.88 0.76 0.55 12.59 12.41 27.19 9.3 1.63 0.62 0.54 9.91 4.91 17.61 5.8
M08 0.48 0.22 0.51 11.61 9.96 22.78 10.2 0.59 0.53 0.38 8.92 10.55 20.97 7.8
M09 0.44 0.37 0.53 8.78 11.81 21.93 7.6 0.54 0.54 0.45 16.55 15.12 33.2 13.5
M10 0.05 0.12 0.29 9.07 7.96 17.49 5.7 0.34 0.2 0.13 7.2 4.36 12.23 4.2
M11 0.09 0.05 0.25 6.14 6.62 13.15 3.2 0.52 0.25 0.23 14.83 5.93 21.76 5.2
M12 0.24 0.1 0.38 18.86 6.89 26.47 4.5 0.29 0.19 0.16 6.29 4.25 11.18 4.2
M13 0.39 0.94 0.72 22.99 20.13 45.17 16.6
M14 0.04 0.39 0.49 13.49 12.86 27.27 5.8
Σ: sum of exchangeable cations, CEC: cationic-exchange capacity.
Table IV.2.6 Semi-quantitative mineralogical composition (mass %, DRX) and specific surface area (m2/g) of Z6V1 samples
Z6V1S1 Z6V1S2a
Sample Sheet Feldspars Sheet Feldspars
Quartz Calcite Dolomite Siderite Hematite Se Quartz Calcite Dolomite Siderite Se
silicates Na K silicates Na K
M01 69 24 3 2 0.8 n.d. 0.8 0.9 32 44 36 6 8 2.1 2.3 0.7 33
M02 63 29 3 2 n.d. n.d. 1.0 1.3 50 49 43 3 3 n.d. 1.8 0.6 39
M03 69 25 3 1 n.d. n.d. 0.5 1.1 56 54 39 1 3 n.d. 1.7 1.0 36
M04 71 23 3 1 n.d. n.d. 0.6 1.2 59 42 50 1 5 n.d. 1.8 0.6 34
M05 74 21 3 1 n.d. n.d. 0.4 0.8 69 42 52 2 1 n.d. 2 0.7 30
M06 72 22 1 3 0.5 n.d. 0.4 0.8 61 42 50 4 3 n.d. 0.6 1.1 28
M07 61 32 3 4 n.d. n.d. 0.4 0.9 47 34 55 6 2 n.d. 2.5 0.6 28
M08 49 40 5 3 n.d. n.d. 1.5 1.9 30 51 40 4 2 n.d. 3.3 0.7 33
M09 42 50 4 1 n.d. n.d. 0.8 1.3 38 60 30 3 5 n.d. 1.4 1.3 66
M10 30 60 8 2 n.d. n.d. 1.1 n.d. 21 18 73 4 3 n.d. 1.5 0.1 4
M11 23 67 5 5 n.d. n.d. 0.3 n.d. 11 33 56 7 2 n.d. 2.6 0.2 12
M12 23 69 6 2 n.d. n.d. 0.6 n.d. 8 28 59 7 4 n.d. 1.2 0.8 11
M13 81 15 2 1 n.d. n.d. 0.5 1.0 80
M14 30 53 4 12 n.d. 0.5 0.7 0.8 36
a
Hematite was not detected in borehole S2. Se: specific surface area, n.d.: no detected
Z6V1S1 Z6V1S2
Sample Sample
Illite Smectite Kaolinite + chlorite Illite Smectite Kaolinite + chlorite
M01 51 8 10 M01 34 4 6
M13 57 15 10 M09 42 13 6
Z6 / V1 / S1
Z6 / V1 / S1
Intensity (a.u.)
Intensidad (u.a.)
(u.a.)
M13
Intensidad
Intensity (a.u.)
M11
M09
M07
M05
M03
M01
2θ (º) 2θ (º)

slides of Z6V1S1M13
involving: drying at room temperature, solvation with glycerol (0.1:2 clay-
to-water+glycerol ratio) and heating at 550ºC for 24 h (0.1:2 clay-to-water)
Z6 / V1 / S2
Z6 / V1 / S2
Intensity (a.u.)
(a.u.) (u.a.)
Intensidad (u.a.)
Intensidad
Intensity
M14
M06
M01
2θ (º) 2θ (º)

slides of Z6V1S2M09
IV.3. Z6V2 landfill
Z6V2S1 Z6V2S2
Sample Sample
(m) (cm) (m) (m) (cm) (m)
M01 28.30-28.325 2.5 0.01 M01 27.000-27.025 2.5 0.01
M02 28.325-28.350 2.5 0.04 M02 27.025-27.050 2.5 0.04
M03 28.35-28.375 2.5 0.06 M03 27.050-27.075 2.5 0.06
M04 28.375-28.40 2.5 0.09 M04 27.075-27.100 2.5 0.09
M05 28.40-28.45 5.0 0.13 M05 27.10-27.15 5.0 0.13
M06 28.45-28.50 5.0 0.18 M06 27.15-27.20 5.0 0.18
M07 28.50-28.60 10.0 0.25 M07 27.20-27.30 10.0 0.25
M08 28.60-28.68 8.0 0.34 M08 27.30-27.40 10.0 0.35
M09 29.25-29.35 10.0 1.00 M09 27.40-27.48 8.0 0.44
M10 29.85-29.95 10.0 1.60 M10 28.00-28.10 10.0 1.05
M11 30.45-30.55 10.0 2.20 M11 28.60-28.70 10.0 1.65
M12 31.55-31.65 10.0 3.30 M12 29.25-29.35 10.0 2.30
M13 32.95-33.05 10.0 4.70 M13 30.42-30.52 10.0 3.47
M14 31.65-31.75 10.0 4.70
a
Z6V2 samples
Z6V2S1 Z6V2S2
Sample
M01 8.3 105 1.600 1070 813 35.91 8.5 168 1.040 388 283 18.82
M02 8.6 127 1.990 612 483 32.42 8.5 154 1.030 373 281 19.79
M03 8.6 129 1.520 374 443 30.91 8.6 139 .940 315 334 18.74
M04 8.6 136 1.610 329 369 33.96 8.4 162 1.250 143 167 38.12
M05 8.6 141 1.460 298 394 33.88 8.4 164 1.070 433 185 40.78
M06 8.5 147 1.650 230 365 37.74 8.4 187 0.982 110 182 31.85
M07 8.5 148 1.270 175 349 38.65 8.3 174 0.918 87 148 38.86
M08 8.4 157 1.100 127 263 38.24 8.4 182 0.678 71 79 39.31
M09 8.4 162 0.701 143 243 42.78 8.3 178 0.700 54 87 40.78
M10 8.4 169 0.525 91 231 39.78 8.5 192 0.390 60 122 30.66
M11 8.5 167 0.378 63 221 42.62 8.9 158 0.272 54 108 19.64
M12 8.4 175 0.306 55 192 33.43 8.8 151 0.386 76 136 22.93
M13 8.5 172 0.498 62 131 32.77 8.9 145 0.235 52 66 30.52
M14 8.9 158 0.197 119 41 24.97
Z6V2S1 Z6V2S2
Sample
M01 93.45 32.91 17.90 13.93 15.17 19.94 98.73 2.11 n.d. 48.87 23.44 12.87 3.01 0.62 2.86 64.32 0.53 n.d.
M02 92.01 23.23 14.82 6.10 5.73 16.50 98.31 1.90 n.d. 44.22 22.68 12.04 2.41 0.53 2.93 56.41 0.30 n.d.
M03 76.06 18.88 13.50 5.17 5.63 16.95 83.47 1.52 n.d. 32.16 17.73 9.11 3.06 1.70 2.78 42.55 0.59 n.d.
M04 68.87 20.37 12.72 4.67 6.24 17.05 78.11 2.10 n.d. 19.49 20.78 3.38 3.94 6.05 4.89 25.53 0.07 n.d.
M05 60.46 19.05 11.87 4.84 6.08 17.29 71.17 1.19 n.d. 0.96 18.88 2.57 5.54 10.02 4.34 30.10 0.11 n.d.
M06 53.70 17.53 10.92 5.19 7.76 20.03 64.97 0.85 n.d. 3.76 15.09 1.92 4.36 8.78 3.86 24.78 0.03 n.d.
M07 41.84 15.63 7.73 5.25 8.26 18.33 62.46 0.62 n.d. 0.51 15.67 2.12 4.59 8.97 3.42 23.58 0.12 n.d.
M08 26.63 12.25 4.88 6.09 10.89 17.45 49.02 0.18 n.d. 0.34 12.32 1.63 3.56 7.36 2.50 16.15 0.04 n.d.
M09 10.68 11.14 2.13 6.71 10.00 8.51 37.81 0.12 n.d. n.d. 9.89 1.51 4.35 10.52 11.62 18.64 0.06 n.d.
M10 4.10 8.74 1.74 6.41 11.37 5.70 32.55 0.11 n.d. n.d. 7.89 1.06 4.01 6.96 5.38 15.97 0.20 n.d.
M11 1.08 6.97 2.25 6.46 13.25 2.93 34.19 0.10 n.d. n.d. 5.57 1.26 3.83 4.98 3.05 14.80 0.04 n.d.
M12 n.d. 0.77 0.62 9.71 11.28 1.23 25.54 0.14 n.d. 2.38 9.71 1.63 5.45 7.46 4.56 42.54 0.06 n.d.
M13 0.78 6.34 2.42 3.76 13.50 2.80 19.50 0.60 n.d. 0.37 4.80 1.47 2.85 5.06 2.32 11.95 0.07 n.d.
M14 1.72 4.20 1.39 2.48 2.90 2.03 7.77 0.07 n.d.

Z6V2S1 Z6V2S2
Sample
M01 188.5 1.285 208.8 285.6 41.9 37.1 93.3 0.047 151.2 49.6 18.7 36.3
M02 113.7 0.606 127.8 75.9 27.6 41.1 102.3 0.036 95.6 54.9 18.4 41.8
M03 96.9 0.686 85.9 60.8 25.0 38.1 94.9 0.082 143.9 52.0 17.5 38.1
M04 101.9 0.657 85.4 63.1 30.6 37.9 149.5 0.158 144.5 83.3 25.3 59.5
M05 100.6 0.585 78.5 75.8 25.8 38.9 136.3 0.187 175.4 88.3 24.4 58.6
M06 109.4 0.799 71.7 60.6 32.2 41.2 141.1 0.329 176.2 83.7 25.3 59.3
M07 112.5 0.500 54.3 62.7 27.6 40.8 139.0 0.334 182.6 84.2 27.2 59.1
M08 119.0 0.500 50.0 63.4 26.5 43.6 141.4 0.472 189.9 83.7 30.0 57.3
M09 121.0 0.523 54.3 67.0 26.0 43.7 140.2 0.645 170.9 86.1 34.3 57.8
M10 121.4 0.403 48.2 67.5 27.2 42.2 139.9 0.619 218.0 90.6 67.4 55.2
M11 115.9 0.827 55.2 62.7 30.5 32.1 85.6 0.044 114.6 54.6 23.0 30.8
M12 92.4 0.528 39.6 57.2 23.7 34.7 66.3 0.028 79.9 36.9 16.9 25.7
M13 122.4 0.400 36.7 74.4 22.5 50.8 70.6 0.023 68.2 38.1 27.2 27.1
M14 75.3 0.015 65.8 44.9 30.0 28.9
Z6V2S1 Z6V2S2
CEC CEC
M01 6.22 0.51 1.68 32.25 27.48 68.14 20.8 4.43 0.73 2.06 12.13 3.55 22.9 8. 5
M02 7.15 1.41 2.5 27.87 24.45 63.38 27.2 4.79 0.63 1.9 6.51 3.26 17.09 9.4
M03 6.41 0.94 2.05 34.09 23.18 66.67 15.1 3.3 0.45 1.03 6.61 7.88 19.27 9.3
M04 5.5 0.6 1.85 33.57 23.68 65.2 19.2 2.24 0.73 0.8 14.67 26.48 44.92 49.5
M05 5.57 0.52 1.9 34.4 24.71 67.1 26.3 0.45 0.86 0.64 24.4 27.24 53.59 47.9
M06 5.18 0.99 2.08 28.57 26.4 63.22 31.4 0.43 0.37 0.65 19.39 24.82 45.66 38.5
M07 6.07 0.62 1.64 21.26 25.91 55.5 39.3 0.33 0.59 0.67 16.6 27.29 45.48 47.7
M08 4.09 0.62 1.22 24.06 28.25 58.24 22.3 0.25 0.79 0.71 12.11 28.61 42.47 49.3
M09 2.2 0.39 0.79 25.53 30.95 59.86 24.7 n.d. 0.43 0.67 11.87 22.4 35.37 52.6
M10 0.99 0.74 0.8 26.54 36.12 65.19 19.9 n.d. 0.08 0.6 21.93 23.7 46.31 44.1
M11 0.58 0.14 0.71 22.81 33.82 58.06 21.7 0.02 0.08 0.28 8.85 10.94 20.17 7.3
M12 0.44 0.46 0.35 30.95 23.03 55.23 13.6 0.22 n.d. 0.28 9.14 13.04 22.68 11.3
M13 0.37 0.24 0.74 13.14 20.37 34.86 13.7 0.11 0.27 0.53 4.01 6.19 11.11 4.4
M14 0.21 0.01 0.23 3.35 4.91 8.71 2.8
Z6V2S1 Z6V2S2
Sample Feldspars e Feldspars
Sheet silicates Quartz Calcite Dolomite S Sheet silicates Quartz Calcite Dolomite Se
Na K Na K
M01 67 22 1 2 7 1.2 48 35 45 14 4 n.d. 1.4 20
M02 92 4 0.4 0.6 2 0.9 75 38 42 15 5 n.d. 1.2 18
M03 89 5 0.6 0.8 4 1.7 75 47 38 9 6 n.d. 0.9 20
M04 86 3 0.5 1 7 2 78 35 48 10 4 1 1.5 75
M05 79 10 0.6 1 7 2.1 71 94 4 0.7 0.7 n.d. 0.4 82
M06 89 4 0.6 0.8 3 1.7 88 93 6 0.6 0.8 n.d. 0.5 87
M07 90 4 0.5 0.9 3.3 1.6 95 97 2 0.2 1.1 n.d. n.d. 86
M08 91 4 0.9 0.7 1.9 2 95 95 3 0.2 1.2 n.d. n.d. 79
M09 96 2 0.2 0.5 0.8 0.7 104 96 3 0.3 0.6 n.d. n.d. 88
M10 95 1 0.5 0.8 0.8 1.4 101 93 5 0.9 0.7 n.d. n.d. 80
M11 94 2 0.3 0.8 0.9 2 103 36 49 4 10 n.d. 1 26
M12 84 4 0.5 0.4 9 2 48 54 31 5 7 n.d. 2 30
M13 92 6 0.7 1.3 n.d. n.d. 80 36 52 5 6 n.d. 0.9 15
M14 29 54 8 8 n.d. 1 11
Se: specific surface area, n.d.: no detected.
Z6V2S1 Z6V2S2
Sample Sample
Illite Smectite Chlorite Illite Smectite Chlorite
M01 45 17 5 M01 24 6 5
M08 61 22 8 M14 20 5 4
Z6 / V2 / S1
Z6 / V2 / S1
(u.a.)
(a.u.) (u.a.)
(a.u.)
Intensidad
Intensidad
Intensity
M13
Intensity
M06
M01
2θ (º)
Fig. IV.3.1 X-ray powder-diffraction patterns (a.u: arbitrary units) of Z6V2S1. 2θ (º)
slides of Z6V2S1M01
Z6 / V2 / S2
(a.u.)
Z6 / V2 / S2
Intensity(u.a.)
Intensidad (u.a.)
Intensidad
Intensity (a.u.)
M14
M06
M01
2θ (º)
Fig. IV.3.3 X-ray powder-diffraction patterns (a.u: arbitrary units) of Z6V2S2. 2θ (º)
slides of Z6V2S2M01
IV.4. Z1V1 landfill
Z1V1S1 Z1V1S2
Sample Sample
(m) (cm) (m) (m) (cm) (m)
M01 7.800-7.825 2.5 0.01 M01 9.800-9.825 2.5 0.01
M02 7.825-7.850 2.5 0.04 M02 9.825-9.850 2.5 0.04
M03 7.850-7.875 2.5 0.06 M03 9.850-9.875 2.5 0.06
M04 7.875-7.900 2.5 0.09 M04 9.875-9.900 2.5 0.09
M05 7.900-7.950 5.0 0.13 M05 9.90-9.95 5.0 0.13
M06 8.00-8.05 5.0 0.23 M06 9.95-10.00 5.0 0.18
M07 8.05-8.15 10.0 0.30 M07 10.00-10.10 10.0 0.25
M08 8.15-8.20 5.0 0.38 M08 10.10-10.15 5.0 0.33
M09 8.20-8.40 20.0 0.50 M09 10.70-10.80 10.0 0.95
M10 8.85-8.95 10.0 1.10 M10 10.80-10.93 13.0 1.07
M11 9.00-9.10 10.0 1.25 M11 10.956-11.050 9.4 1.20
M12 9.10-9.20 10.0 1.35 M12 12.28-12.36 8.0 2.52
M13 9.40-9.50 10.0 1.65 M13 13.37-13.49 12.0 3.63
a
M14 9.80-9.90 10.0 2.05 Depths measured from the surface (i.e., including the waste), b
M15 10.10-10.20 10.0 2.35 Average depth measured from the waste bottom
.
Z1V1 samples
Z1V1S1 Z1V1S2
Sample
M01 4.9 241 0.121 240 2 19.31 7.4 193 2.25 185 190 22.98
M02 5 237 0.094 252 2 19.01 6.7 219 0.846 115 66 22.73
M03 4.7 253 0.101 167 2 20.14 6.7 201 0.481 124 80 24.97
M04 4.7 258 0.091 136 3 20.87 6.6 182 0.288 127 50 26.78
M05 4.8 267 0.088 96 3 18.87 6.3 169 0.271 195 39 35.69
M06 5 233 0.111 392 4 20.1 6.2 173 0.415 186 36 43.35
M07 5.1 232 0.097 384 5 16.93 6.1 176 0.401 165 33 37.02
M08 5.5 245 0.112 45 2 16.17 5.9 182 0.536 151 24 34.23
M09 5.8 233 0.262 48 11 18.33 5.9 167 0.156 132 20 25.94
M10 5.1 228 0.174 417 7 24.56 6.5 171 0.267 96 21 27.58
M11 4.5 350 0.196 34 2 14.88 7.5 145 0.038 44 27 9.55
M12 4.5 323 0.138 30 1 19.72 8.8 128 0.069 106 18 10
M13 4.4 325 0.142 34 1 17.17 9 113 0.062 118 21 9.69
M14 5.2 300 0.052 62 2 12.07
M15 5.6 290 0.048 103 2 11.58

Z1V1S1 Z1V1S2
Sample
M01 0.95 3.79 6.28 1.17 n.d. 0.15 n.d. n.d. n.d. 2.74 3.59 1.92 81.36 3.11 n.d. 16.78 2.65 n.d.
M02 1.16 3.73 3.62 n.d. n.d. 1.35 n.d. n.d. n.d. 3.12 1.77 1.5 49.07 2.44 0.17 9 2.65 n.d.
M03 0.76 4.86 4.79 n.d. 0.84 0.26 n.d. n.d. n.d. 3.23 2.89 2.83 7.03 0.45 0.5 1.92 1.56 n.d.
M04 0.64 2.23 1.99 n.d. n.d. 0.26 n.d. n.d. n.d. 3.42 2.79 3.84 4.68 0.66 1.11 1.22 1.4 n.d.
M05 0.5 2.42 0.94 n.d. n.d. 0.18 n.d. n.d. n.d. 3.34 4.54 5.89 5.54 0.42 1.2 4.46 1.09 n.d.
M06 2.41 2.22 5.35 2.1 n.d. 0.29 n.d. n.d. n.d. 3.03 4.99 2.33 11.97 1.42 0.5 4.68 1.61 n.d.
M07 2.31 3.6 4.39 n.d. n.d. 0.18 n.d. n.d. n.d. 4.25 3.78 1.71 5.93 0.57 0.45 n.d. 1.82 n.d.
M08 0.36 2.9 0.54 n.d. 0.66 n.d. n.d. n.d. n.d. 1.94 3.52 1.47 10.84 0.9 0.21 n.d. 2.71 n.d.
M09 n.d. 0.91 0.67 n.d. 1.62 n.d. n.d. n.d. n.d. 0.27 2.46 1.86 3.8 0.31 0.95 2.05 1.35 n.d.
M10 2.66 7.63 5.39 2.71 n.d. 0.15 n.d. 0.11 n.d. 0.49 1.77 1.28 16.66 1.62 0.37 3.4 1.51 n.d.
M11 n.d. 0.64 0.41 n.d. 0.71 1.24 n.d. 0.03 n.d. n.d. 0.96 0.22 1.85 0.44 0.87 1.92 0.21 n.d.
M12 n.d. 1.33 0.63 n.d. 1.08 1.13 n.d. 0.02 n.d. n.d. 0.91 0.6 2.46 0.41 1.11 2.49 n.d. n.d.
M13 n.d. 1.04 0.61 n.d. 0.96 1.1 n.d. n.d. n.d. n.d. 0.71 0.6 3.03 0.5 1.03 2.64 n.d. n.d.
M14 n.d. 3.85 1 n.d. n.d. 1.02 n.d. n.d. n.d.
M15 n.d. 2.29 3.45 1.58 n.d. 0.95 n.d. 0.05 n.d.

Z1V1S1 Z1V1S2
Sample
M01 94.9 0.145 48.7 57.7 15.6 12.3 4049.6 41.753 259.6 182.1 36.8 26.9
M02 93.0 0.130 37.5 61.0 14.0 12.6 1426.9 3.536 116.1 51.0 17.3 23.0
M03 113.6 0.167 36.9 69.6 15.7 16.7 384.1 1.168 39.8 47.7 14.9 23.4
M04 165.7 0.145 45.7 74.4 21.0 17.1 184.5 0.793 27.8 49.9 17.7 25.0
M05 197.4 0.191 74.6 74.5 29.8 20.9 190.5 1.270 26.4 51.1 20.2 26.2
M06 90.4 0.067 44.3 84.4 19.8 16.5 253.6 1.919 37.5 49.8 24.0 27.8
M07 82.5 0.105 36.3 68.6 15.1 11.9 209.0 1.556 36.9 42.7 23.7 22.8
M08 165.3 0.168 42.4 52.2 56.9 12.6 459.1 0.850 48.2 44.1 27.8 22.8
M09 117.8 0.123 27.0 45.0 38.8 11.9 83.9 0.149 18.5 34.1 20.6 18.1
M10 100.5 0.095 33.0 69.0 25.9 18.4 102.2 0.222 14.0 34.1 23.2 17.5
M11 130.9 0.475 32.7 56.0 25.9 10.9 13.6 0.012 n.d. 7.3 5.0 1.0
M12 107.8 0.205 33.1 88.6 29.6 21.2 19.7 0.019 7.6 10.7 4.4 2.6
M13 117.1 0.328 24.4 110.4 21.4 27.0 37.1 0.0 8.0 21.4 3.4 3.1
M14 101.8 0.2 19.0 80.5 14.4 27.1
M15 103.4 0.2 14.5 97.6 7.2 25.8
Z1V1S1 Z1V1S2
CEC CEC
M01 0.17 0.07 0.07 0.96 0.41 1.68 8.5 0.24 0.04 0.22 23.34 0.82 24.66 6.6
M02 0.27 0.04 0.07 0.84 0.4 1.62 12.1 0.21 0.03 0.18 13.09 0.65 14.16 6.5
M03 0.2 0.25 0.09 0.75 0.27 1.56 7.4 0.28 0.03 0.16 6.46 0.93 7.86 7.5
M04 0.13 0.21 0.08 0.7 0.3 1.42 9.1 0.29 0.04 0.19 6.32 1.21 8.05 5.1
M05 0.3 0.12 0.12 0.68 0.49 1.71 9.2 0.4 0.06 0.29 8.71 1.55 11.01 10.0
M06 0.61 0.24 0.08 0.66 0.31 1.9 6.7 0.24 0.08 0.13 10.8 1.51 12.76 14.4
M07 0.55 0.12 0.11 n.d. n.d. 0.78 3.2 0.2 0.05 0.1 8.92 1.38 10.65 9.7
M08 0.28 0.5 0.17 1.12 0.71 2.78 6.9 0.15 0.01 0.09 8.9 1.14 10.29 10.8
M09 0.09 0.03 0.12 1.23 0.75 2.22 4.9 0.03 0.04 0.09 7.11 1.18 8.45 6.0
M10 0.55 0.12 0.12 1.43 0.9 3.12 8.3 0.04 0.03 0.08 9.1 1.04 10.29 6.2
M11 0.02 0.08 0.09 0.44 0.96 1.59 7.2 n.d. 0.02 0.08 0.73 0.14 0.97 0.5
M12 0.03 0.07 0.11 1 1.02 2.23 6.4 n.d. 0.03 0.02 2.2 0.28 2.53 0.5
M13 0.01 0.12 0.11 0.61 1.64 2.49 10.9 n.d. n.d. 0.01 6.85 0.23 7.09 0.8
M14 0.02 0.07 0.13 1.98 3.61 5.81 6.0
M15 n.d. 0.11 0.39 2.34 2.13 4.97 6.1
Σ: sum of exchangeable cations, CEC: cationic-exchange capacity.
Z1V1S1 Z1V1S2
Feldspar
Sample Feldspars
Sheet silicates Quartz Calcite Dolomite Se Sheet silicates Quartz s Calcite Dolomite Se
Na K Na K
M01 31 66 1.8 1.1 n.d. n.d. 12 23 75 1.6 0.6 n.d. n.d. 8
M02 40 58 1.5 0.9 n.d. n.d. 13 27 70 1.2 2.1 n.d. n.d. 8
M03 44 55 0.8 0.3 n.d. n.d. 16 27 69 3 0.2 n.d. n.d. 8
M04 44 54 1.4 0.6 n.d. n.d. 18 35 62 2 0.8 n.d. n.d. 9
M05 43 56 0.3 0.5 n.d. n.d. 18 39 59 1.3 0.8 n.d. n.d. 12
M06 33 64 2 0.8 n.d. n.d. 12 29 67 3 0.5 0.2 n.d. 8
M07 35 63 1.5 0.4 n.d. n.d. 12 34 65 0.5 n.d. n.d. n.d. 8
M08 24 69 1.5 5 n.d. n.d. 15 30 67 2.3 1.2 n.d. n.d. 8
M09 22 77 0.8 0.5 n.d. n.d. 8 24 75 1.5 n.d. n.d. n.d. 6
M10 34 63 2 0.9 n.d. n.d. 9 29 69 1.0 0.7 n.d. n.d. 7
M11 36 63 0.8 0.5 n.d. n.d. 13 7 90 3 n.d. n.d. n.d. 3
M12 46 52 1.4 1.1 n.d. n.d. 20 10 83 7 n.d. n.d. n.d. 2
M13 68 30 1.1 0.5 n.d. n.d. 19 12 84 4 n.d. n.d. n.d. 2
M14 35 63 1.0 1.3 n.d. n.d. 12
M15 37 59 3 0.8 0.3 0.1 13
Se: specific surface area, n.d.: no detected
Z1V1S1 Z1V1S2
Sample Sample
Illite Kaolinite Illite Kaolinite
M01 11 20 M01 12 11
M02 16 24 M03 14 13
M04 17 27 M06 17 12
M08 9 15 M10 11 18
M13 36 32 M12 4 6
M15 27 10
Z1 / V1 / S1
(a.u.)
Z1 / V1 / S1
Intensidad (u.a.)
(u.a.)
Intensity
Intensity (a.u.)
Intensidad
M15
M13
M11
M09
M07
M05
M03
M01
2θ (º)
2θ (º)

slides of Z1V1S1M13
involving: drying at room temperature, solvation with glycerol (0.1:2 clay-
to-water+glycerol ratio) and heating at 550ºC for 24 h (0.1:2 clay-to-water)
Z1 / V1 / S2
Z1 / V1 / S2
(a.u.) (u.a.)
Intensity (a.u.)
(u.a.)
Intensidad
Intensidad
M13
M11
Intensity
M09
M07
M05
M03
M01
2θ (º) 2θ (º)

slides of Z1V1S2M03
IV.5. Z5V1 landfill

Minimum & Minimum & Minimum &
Average Average Average
maximum Thickness maximum Thickness maximum Thickness
Sample depthb Sample depthb Sample depthb
depthsa (cm) depthsa (cm) depthsa (cm)
(m) (cm) (m)
(m) (m) (m)
M01 6.20-6.25 5 0.03 M01 15.00-15.04 4 0.02 M01 13.60-13.63 3 0.02
M02 6.25-6.30 5 0.08 M02 15.04-15.065 2.5 0.05 M02 13.63-13.66 3 0.05
M03 6.30-6.34 4 0.12 M03 15.065-15.09 2.5 0.08 M03 13.66-13.69 3 0.08
M04 6.34-6.40 6 0.17 M04 15.09-15.15 6 0.12 M04 13.69-13.72 3 0.11
M05 6.70-7.40 70 0.85 M05 15.15-15.25 10 0.20 M05 13.72-13.82 10 0.17
M06 7.40-8.50 110 1.75 M06 15.25-15.35 10 0.30 M06 13.82-13.92 10 0.27
M07 15.55-15.80 25 0.68 M07 14.12-14.22 10 0.57
M08 14.60-14.70 10 1.05
M09 15.25-15.35 10 1.70
a
Table IV.5.2 pH, redox potential (Eh: mv), electrical conductivity (EC: mS/cm), water soluble organic/inorganic carbon (WSOC/WSIC: µg/g), moisture
(h: %) of Z5V1 samples

Sample
pH Eh EC WSOC WSIC h pH Eh EC WSOC WSIC h pH Eh EC WSOC WSIC h
M01 8.4 127 2.55 649 395 26.58 8.5 115 2.3 1115 406 15.74 8.2 134 2.53 1034 378 31.47
M02 8.7 110 1.78 541 294 12.13 8.6 108 2.72 1269 334 28.84 8.3 120 2.79 1214 375 19.57
M03 8.5 119 2.35 1376 305 13.17 8.6 105 2.53 1055 410 25.69 8.4 111 2.52 365 169 18.39
M04 8.5 120 2.47 1139 402 18.63 8.6 107 2.58 907 394 27.75 8.5 109 2.43 702 394 19.62
M05 8.4 115 1.54 402 255 10.66 8.6 136 2.42 939 422 24.57 8.6 103 2.42 713 480 25.36
M06 6.8 214 2.64 2598 13 9.48 8.6 131 2.46 596 486 22.7 8.6 112 2.34 349 203 29.07
M07 8.4 140 2.07 374 322 16.5 8.3 130 2.17 416 257 17.58
M08 7.7 179 1.02 73 70 13.23
M09 7.7 172 0.91 84 120 16.81

Soluble Soluble
Soluble cations Soluble anions Soluble cations Soluble cations
Sample anions anions
NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk
M01 76.16 55.02 14.96 1.93 0.2 5.17 102.26 82.97 37.37 12.71 0.01 n.d. 3.23 91.45 129.02 71.09 29.4 2.93 n.d. 3.62 162.44
M02 44.12 33.18 4.83 0.16 n.d. 2.9 58.12 126.75 52.36 23.43 0.65 n.d. 4.07 141.85 96.17 45.89 21.74 0.88 0.05 4.72 122.58
M03 65.91 41.99 15.72 0.08 n.d. 4.13 101.73 106.7 47.56 18.77 0.22 n.d. 3.86 123.63 83.48 40.26 22.56 1.15 n.d. 1.63 118.13
M04 64.92 42.75 20.95 0.56 n.d. 3.76 119.44 106.2 52.81 25.4 0.34 n.d. 3.4 124.5 76.07 42.93 20.41 1.11 0.01 3.99 146.95
M05 48.21 26.35 8.98 0.61 n.d. 2.05 63.31 71.45 51.3 18.53 n.d. n.d. 3 107.63 73.07 57.07 11.8 0.39 0.41 3.95 120.4
M06 n.d. 23.88 0.43 6.55 16.48 1.46 35.54 66.68 55.02 17.11 0.2 0.84 4.16 96.85 79.28 32.31 7.41 2.42 n.d. 1.94 96.04
M07 22.25 46.8 5.12 5.94 17.23 3.26 20.14 28.88 38.48 4.54 6.61 0.87 4.2 33.19
M08 n.d. 8.22 0.75 14.58 3.22 1.89 8.88
M09 0.24 5.04 1.18 16.58 3.32 1.67 10.19
Alk: alkalinity, n.d.: no detected. SO42- concentrations no detected in this substratum.
Table IV.5.4 Heavy metals (µg/g) and iron (mg/g) of Z5V1 samples

Sample
Zn Cd Pb Cr Cu Fe Zn Cd Pb Cr Cu Fe Zn Cd Pb Cr Cu Fe
M01 144.3 0.331 145.6 129.5 49.1 34.8 4.9 2.874 57.0 125.0 25.5 271.1 2.9 3.493 41.2 106.4 26.6 328.3
M02 38.3 0.030 10.4 84.4 5.3 25.5 3.2 1.534 30.4 146.1 16.7 225.6 3.2 1.069 36.3 107.0 19.8 343.0
M03 54.0 0.078 10.6 96.2 7.3 29.2 2.7 0.400 22.7 142.4 13.2 207.7 4.8 4.149 27.0 113.1 15.1 306.6
M04 68.3 0.108 13.2 129.0 12.4 28.5 2.9 0.520 23.2 126.7 15.8 202.3 3.1 2.886 4.1 97.9 6.1 228.0
M05 39.2 0.017 4.6 82.9 8.9 23.5 2.0 0.150 18.2 140.6 12.9 200.8 0.6 5.687 12.4 151.2 17.2 229.4
M06 49.6 0.028 6.9 89.5 9.3 33.0 1.2 0.105 14.7 137.9 21.5 191.5 0.6 2.638 10.2 202.8 18.7 235.7
M07 2.2 0.404 27.5 60.9 28.3 271.4 1.0 0.998 10.2 90.5 13.2 284.1
M08 0.7 4.506 12.3 181.6 22.5 329.4
M09 0.7 2.911 5.7 143.6 23.1 356.2

Sample Exchangeable cations CEC Exchangeable cations CEC Exchangeable cations CEC
NH4+ Na+ K+ Ca2+ Mg2+ Σ NH4+ Na+ K+ Ca2+ Mg2+ Σ NH4+ Na+ K+ Ca2+ Mg2+ Σ
M01 6.11 1.21 1.89 14.95 3.24 27.4 11.0 6.33 1 1 9.18 0.63 18.14 12.0 5.95 1.48 3.08 4.77 1.8 17.08 9.6
M02 4.41 1.1 1.09 7.66 1.56 15.82 7.1 10.82 1.9 1.9 8.84 1.01 24.47 18.4 6.42 0.79 1.88 11.7 1.22 22.01 73.2
M03 4.82 0.84 2.78 6.04 0.26 14.74 7.6 9.1 2.03 2.03 8.19 1.05 22.4 14.0 5.93 0.63 2.33 13.37 1.15 23.41 61.4
M04 7.08 1.16 3.29 7.5 0.36 19.39 13.3 9.75 2.02 2.02 8.46 1.14 23.39 17.0 4.67 0.42 1.93 27.77 1.17 35.96 42.0
M05 5.01 0.93 1.76 n.d. 0.25 7.95 7.5 7.39 2.2 2.2 16.38 6.65 34.82 21.3 9.76 3.03 2.66 21.52 4.09 41.06 88.9
M06 0.42 0.18 0.04 13.47 4.27 18.38 10.5 7.78 2.04 2.04 15.58 4.11 31.55 20.3 7.87 2.15 1.34 42.03 9.77 63.16 18.2
M07 1.92 0.8 0.8 22.55 4.53 30.6 15.5 2.42 0.65 0.66 34.01 19.57 57.31 6.6
M08 0.1 0.07 0.14 32.97 18.97 52.25 13.5
M09 0.21 0.1 0.15 29.28 23.42 53.16 9.6
Table IV.5.6 Semi-quantitative average mineralogical composition (mass %, DRX) and specific surface area (m2/g) of Z5V1 samples
Z5V1S1 Z5V1S2
Sample Feldspars Feldspars
Sheet silicates Quartz Calcite Dolomite Pyrite Se Sheet silicates Quartz Calcite Dolomite Pyrite Se
Na K Na K
M01 33 50 11 1.1 4 0.9 0.4 7 32 50 12 n.d. 6 0.4 n.d. 9
M02 4 94 2 0.1 n.d. n.d. n.d. 8 50 15 1 n.d. 34 n.d. n.d. 23
M03 60 21 14 1.3 3 0.6 n.d. 4 41 10 0 n.d. 49 n.d. n.d. 23
M04 50 28 8 0.7 13 0.2 n.d. 10 42 13 1 0.5 44 n.d. n.d. 25
M05 30 54 12 2 n.d. 0.9 0.3 5 49 8 1 0.5 42 n.d. n.d. 26
M06 27 64 9 0.4 n.d. 0.5 n.d. 8 45 10 0 0.3 44 n.d. n.d. 24
M07 43 22 23 5.7 5 1.4 0.5 6
Z5V1S3
Sample Feldspars
Sheet silicates Quartz Calcite Dolomite Pyrite Se
Na K
M01 36 46 13 1.1 3.2 0.5 0.4 5
M02 29 57 10 1.7 1.3 0.6 n.d. 6
M03 35 54 6 1.1 3.3 0.5 n.d. 8
M04 29 45 18 1.5 6.9 0.3 n.d. 5
M05 51 10 1 0.4 37.4 n.d. n.d. 33
M06 50 13 1 0.5 35.4 n.d. n.d. 33
M07 32 47 15 1.2 4.9 n.d. n.d. 6
M08 49 38 10 1.8 n.d. 0.8 n.d. 18
M09 26 64 8 0.8 n.d. 0.5 n.d. 16

Sample Sample Sample
Illite Smectite Chlorite Illite Smectite Chlorite Illite Smectite Chlorite
M01 20 11 2 M01 11 17 4 M01 13 26 7
M04 16 30 4 M02 20 22 8 M02 7 21 1
M06 7 18 2 M07 11 0 32 M05 30 15 6
Z5 / V1 / S1
Intensidad (a.u.)
Intensity (u.a.)
Intensity (a.u.)
M05
M03
M01
2θ (º)
Fig. IV.5.2 X-ray diffraction patterns (a.u: arbitrary units) of

oriented slides of Z5V1S1M04
involving: drying at room temperature, solvation with glycerol (0.1:2
clay-to-water+glycerol ratio) and heating at 550ºC for 24 h (0.1:2 clay-to-
water) (Moore and Reynolds, 1997).
Z5 / V1 / S2
(a.u.)
Intensity(u.a.)
Intensity (a.u.)
Intensidad
M07
M05
M03
M01
2θ (º)

slides of Z5V1S2M07
Z5 / V1 / S3
Intensity
Intensidad (a.u.)
(u.a.)
Intensity (a.u.)
M05
M03
M01
2θ (º)
Fig. IV.5.6 X-ray diffraction patterns (a.u: arbitrary units) of

oriented slides of Z5V1S3M02
involving: drying at room temperature, solvation with glycerol (0.1:2
clay-to-water+glycerol ratio) and heating at 550ºC for 24 h (0.1:2 clay-to-
water) (Moore and Reynolds, 1997).
PCA & VARIMAX ROTATION. APPENDIX V
APPENDIX V. PRINCIPAL COMPONENT ANALYSIS FOLLOWED BY

A VARIMAX ROTATION
Table V.1. Correlation matrix of the 34 variables (1 out of 3)
pH Eh EC WSOC WSIC h Sol_NH4 Sol_Na Sol_K Sol_Ca Sol_Mg Sol_Cl 

pH 1 -0.712 0.260 0.066 0.309 0.053 0.267 0.210 0.208 0.092 0.254 0.167 …
Eh -0.712 1 -0.384 -0.342 -0.363 -0.090 -0.501 -0.314 -0.487 -0.014 -0.164 -0.272 …
EC 0.260 -0.384 1 0.159 0.740 0.088 0.092 0.973 0.208 0.100 0.378 0.950 …
WSOC 0.066 -0.342 0.159 1 0.171 -0.078 0.650 0.059 0.662 -0.101 -0.023 -0.029 …
WSIC 0.309 -0.363 0.740 0.171 1 0.222 0.299 0.737 0.351 0.059 0.292 0.656 …
h 0.053 -0.090 0.088 -0.078 0.222 1 0.137 0.077 0.121 0.094 0.346 0.052 …
Sol_NH4 +
0.267 -0.501 0.092 0.650 0.299 0.137 1 -0.006 0.938 -0.115 -0.181 -0.131 …
Sol_Na +
0.210 -0.314 0.973 0.059 0.737 0.077 -0.006 1 0.124 0.061 0.398 0.973 …
Sol_K+ 0.208 -0.487 0.208 0.662 0.351 0.121 0.938 0.124 1 -0.128 -0.158 0.003 …
Sol_Ca 2+
0.092 -0.014 0.100 -0.101 0.059 0.094 -0.115 0.061 -0.128 1 0.192 0.079 …
Sol_Mg 2+
0.254 -0.164 0.378 -0.023 0.292 0.346 -0.181 0.398 -0.158 0.192 1 0.398 …
Sol_Cl -
0.167 -0.272 0.950 -0.029 0.656 0.052 -0.131 0.973 0.003 0.079 0.398 1 …
Alk 0.367 -0.563 0.162 0.681 0.342 0.164 0.957 0.059 0.927 -0.112 -0.095 -0.067 …
Sol_SO4 2-
0.282 -0.056 0.450 -0.198 0.417 0.065 -0.147 0.413 -0.097 0.291 0.206 0.397 …
Sol_F -
0.148 -0.166 0.870 -0.060 0.730 0.052 -0.146 0.929 -0.018 0.076 0.350 0.931 …
Ex_NH4 +
0.254 -0.484 0.063 0.620 0.285 0.171 0.951 -0.036 0.873 -0.149 -0.178 -0.158 …
Ex_Na+ 0.276 -0.345 0.936 0.116 0.726 0.120 0.117 0.903 0.207 -0.015 0.227 0.873 …
Ex_K +
0.360 -0.508 0.228 0.555 0.433 0.221 0.867 0.136 0.872 -0.134 -0.065 0.019 …
Ex_Ca 2+
0.526 -0.232 0.365 -0.109 0.310 0.069 -0.034 0.357 -0.080 0.138 0.266 0.364 …
Ex_Mg 2+
0.412 -0.097 -0.025 -0.224 0.165 0.551 -0.074 -0.027 -0.161 0.017 0.471 -0.013 …
CEC 0.206 -0.131 0.080 0.121 0.182 0.413 0.246 0.043 0.231 -0.136 0.143 -0.010 …
Sheet silicates 0.232 0.037 -0.055 -0.089 0.128 0.579 0.082 -0.069 0.035 -0.117 0.313 -0.078 …
Qtz -0.444 0.180 -0.203 -0.053 -0.351 -0.483 -0.243 -0.181 -0.212 0.162 -0.349 -0.138 …
Nfs 0.186 -0.253 0.015 0.297 -0.006 -0.310 0.219 -0.027 0.249 -0.039 -0.058 -0.086 …
Kfs 0.256 -0.208 0.039 -0.121 -0.085 -0.183 -0.068 0.048 -0.049 0.030 0.240 0.073 …
Cal 0.292 -0.303 0.518 0.220 0.481 -0.006 0.270 0.516 0.292 -0.094 0.066 0.463 …
Dol 0.358 -0.052 -0.021 -0.150 0.061 -0.008 -0.016 -0.047 -0.086 -0.037 0.052 -0.035 …
SSA 0.285 -0.046 -0.143 -0.169 0.063 0.626 0.054 -0.157 -0.031 -0.061 0.349 -0.153 …
Zn -0.120 0.131 -0.006 -0.098 -0.039 0.058 -0.136 -0.046 -0.136 0.686 -0.004 -0.023 …
Cd -0.055 0.019 -0.002 0.017 -0.008 0.031 0.034 -0.063 0.019 0.607 -0.050 -0.069 …
Pb 0.153 -0.042 -0.093 -0.056 0.056 0.403 0.101 -0.120 0.067 0.298 0.167 -0.127 …
Cr 0.090 -0.122 0.626 0.252 0.617 0.166 0.219 0.560 0.263 0.064 0.113 0.505 …
Cu 0.196 0.033 0.527 -0.239 0.492 0.237 -0.165 0.595 -0.125 0.200 0.463 0.573 …
Fe 0.155 -0.274 0.048 0.376 0.107 -0.016 0.527 -0.027 0.497 -0.085 -0.120 -0.127 …
Eh: redox potential, EC: electrical conductivity, WSOC: water soluble organic carbon, WSIC: water soluble
inorganic carbon, h: moisture, Sol_NH4+: soluble ammonium, Sol_Na+: soluble sodium, Sol_K+: soluble
potassium, Sol_Ca2+: soluble calcium, Sol_Mg2+: soluble magnesium, Sol_Cl-: soluble chloride, Alk: alkalinity,
Sol_SO42-: soluble sulphate, Sol_F-: soluble fluoride, Ex_NH4+: exchangeable ammonium, Ex_Na+:
exchangeable sodium, Ex_K+: exchangeable potassium, Ex_Ca2+: exchangeable calcium, Ex_Mg2+:
exchangeable magnesium, CEC: cationic exchange capacity, Qtz: quartz, Nafs: Na-feldspar, Kfs: K-feldspar,
Cal: calcite, Dol: dolomite, SSA: specific surface area.
APPENDIX V. PCA & VARIMAX ROTATION
Sheet
 Alk Sol_SO42- Sol_F- Ex_NH4+ Ex_Na+ Ex_K+ Ex_Ca2+ Ex_Mg2+ CEC 
silicates
pH … 0.367 0.282 0.148 0.254 0.276 0.360 0.526 0.412 0.206 0.232 …
Eh … -0.563 -0.056 -0.166 -0.484 -0.345 -0.508 -0.232 -0.097 -0.131 0.037 …
EC … 0.162 0.450 0.870 0.063 0.936 0.228 0.365 -0.025 0.080 -0.055 …
WSOC … 0.681 -0.198 -0.060 0.620 0.116 0.555 -0.109 -0.224 0.121 -0.089 …
WSIC … 0.342 0.417 0.730 0.285 0.726 0.433 0.310 0.165 0.182 0.128 …
h … 0.164 0.065 0.052 0.171 0.120 0.221 0.069 0.551 0.413 0.579 …
Sol_NH4+ … 0.957 -0.147 -0.146 0.951 0.117 0.867 -0.034 -0.074 0.246 0.082 …
Sol_Na+
… 0.059 0.413 0.929 -0.036 0.903 0.136 0.357 -0.027 0.043 -0.069 …
Sol_K +
… 0.927 -0.097 -0.018 0.873 0.207 0.872 -0.080 -0.161 0.231 0.035 …
Sol_Ca2+ … -0.112 0.291 0.076 -0.149 -0.015 -0.134 0.138 0.017 -0.136 -0.117 …
Sol_Mg2+ … -0.095 0.206 0.350 -0.178 0.227 -0.065 0.266 0.471 0.143 0.313 …
Sol_Cl -
… -0.067 0.397 0.931 -0.158 0.873 0.019 0.364 -0.013 -0.010 -0.078 …
Alk … 1 -0.142 -0.097 0.927 0.178 0.907 0.032 0.001 0.350 0.149 …
Sol_SO42- … -0.142 1 0.390 -0.189 0.455 -0.058 0.160 0.055 -0.131 -0.003 …
Sol_F- … -0.097 0.390 1 -0.170 0.813 0.019 0.357 0.007 0.012 -0.054 …
Ex_NH4 +
… 0.927 -0.189 -0.170 1 0.121 0.877 -0.041 -0.029 0.308 0.131 …
Ex_Na +
… 0.178 0.455 0.813 0.121 1 0.283 0.391 0.024 0.137 0.066 …
Ex_K+ … 0.907 -0.058 0.019 0.877 0.283 1 0.055 0.089 0.375 0.270 …
Ex_Ca 2+
… 0.032 0.160 0.357 -0.041 0.391 0.055 1 0.479 0.260 0.319 …
Ex_Mg 2+
… 0.001 0.055 0.007 -0.029 0.024 0.089 0.479 1 0.423 0.803 …
CEC … 0.350 -0.131 0.012 0.308 0.137 0.375 0.260 0.423 1 0.487 …
Sheet silicates… 0.149 -0.003 -0.054 0.131 0.066 0.270 0.319 0.803 0.487 1 …
Qtz … -0.335 -0.038 -0.165 -0.310 -0.326 -0.442 -0.517 -0.707 -0.526 -0.876 …
Nfs … 0.243 -0.079 -0.103 0.145 -0.096 0.224 -0.134 -0.263 -0.110 -0.372 …
Kfs … -0.063 0.103 -0.007 -0.111 -0.040 -0.056 -0.007 -0.056 -0.199 -0.225 …
Cal … 0.314 0.055 0.494 0.348 0.576 0.299 0.446 -0.067 0.191 -0.034 …
Dol … -0.008 0.184 -0.043 -0.019 0.057 0.024 0.435 0.319 0.096 0.246 …
SSA … 0.114 0.012 -0.147 0.130 -0.050 0.212 0.206 0.867 0.462 0.881 …
Zn … -0.135 0.019 -0.017 -0.139 -0.077 -0.143 0.018 -0.086 -0.078 -0.087 …
Cd … 0.050 -0.043 -0.060 0.030 -0.067 0.004 0.032 -0.088 0.048 -0.096 …
Pb … 0.087 0.074 -0.134 0.063 -0.103 0.110 -0.069 0.363 0.233 0.372 …
Cr … 0.267 0.295 0.503 0.231 0.700 0.318 0.343 0.108 0.251 0.134 …
Cu … -0.145 0.426 0.622 -0.206 0.455 -0.091 0.403 0.256 0.101 0.167 …
Fe … 0.544 -0.184 -0.115 0.501 0.051 0.409 0.070 -0.003 0.381 -0.032 …
 Qtz Nfs Kfs Cal Dol SSA Zn Cd Pb Cr Cu Fe

pH … -0.444 0.186 0.256 0.292 0.358 0.285 -0.120 -0.055 0.153 0.090 0.196 0.155
Eh … 0.180 -0.253 -0.208 -0.303 -0.052 -0.046 0.131 0.019 -0.042 -0.122 0.033 -0.274
EC … -0.203 0.015 0.039 0.518 -0.021 -0.143 -0.006 -0.002 -0.093 0.626 0.527 0.048
WSOC … -0.053 0.297 -0.121 0.220 -0.150 -0.169 -0.098 0.017 -0.056 0.252 -0.239 0.376
WSIC … -0.351 -0.006 -0.085 0.481 0.061 0.063 -0.039 -0.008 0.056 0.617 0.492 0.107
h … -0.483 -0.310 -0.183 -0.006 -0.008 0.626 0.058 0.031 0.403 0.166 0.237 -0.016
Sol_NH4+ … -0.243 0.219 -0.068 0.270 -0.016 0.054 -0.136 0.034 0.101 0.219 -0.165 0.527
Sol_Na+ … -0.181 -0.027 0.048 0.516 -0.047 -0.157 -0.046 -0.063 -0.120 0.560 0.595 -0.027
Sol_K+ … -0.212 0.249 -0.049 0.292 -0.086 -0.031 -0.136 0.019 0.067 0.263 -0.125 0.497
Sol_Ca2+ … 0.162 -0.039 0.030 -0.094 -0.037 -0.061 0.686 0.607 0.298 0.064 0.200 -0.085
Sol_Mg2+ … -0.349 -0.058 0.240 0.066 0.052 0.349 -0.004 -0.050 0.167 0.113 0.463 -0.120
Sol_Cl- … -0.138 -0.086 0.073 0.463 -0.035 -0.153 -0.023 -0.069 -0.127 0.505 0.573 -0.127
Alk … -0.335 0.243 -0.063 0.314 -0.008 0.114 -0.135 0.050 0.087 0.267 -0.145 0.544
Sol_SO42- … -0.038 -0.079 0.103 0.055 0.184 0.012 0.019 -0.043 0.074 0.295 0.426 -0.184
Sol_F- … -0.165 -0.103 -0.007 0.494 -0.043 -0.147 -0.017 -0.060 -0.134 0.503 0.622 -0.115
Ex_NH4+ … -0.310 0.145 -0.111 0.348 -0.019 0.130 -0.139 0.030 0.063 0.231 -0.206 0.501
Ex_Na+ … -0.326 -0.096 -0.040 0.576 0.057 -0.050 -0.077 -0.067 -0.103 0.700 0.455 0.051
Ex_K+ … -0.442 0.224 -0.056 0.299 0.024 0.212 -0.143 0.004 0.110 0.318 -0.091 0.409
Ex_Ca2+ … -0.517 -0.134 -0.007 0.446 0.435 0.206 0.018 0.032 -0.069 0.343 0.403 0.070
Ex_Mg2+ … -0.707 -0.263 -0.056 -0.067 0.319 0.867 -0.086 -0.088 0.363 0.108 0.256 -0.003
CEC … -0.526 -0.110 -0.199 0.191 0.096 0.462 -0.078 0.048 0.233 0.251 0.101 0.381
Sheet silicates … -0.876 -0.372 -0.225 -0.034 0.246 0.881 -0.087 -0.096 0.372 0.134 0.167 -0.032
Qtz … 1 0.248 0.141 -0.403 -0.308 -0.716 0.166 0.123 -0.201 -0.334 -0.274 -0.157
Nfs … 0.248 1 0.309 -0.188 0.011 -0.385 -0.120 -0.006 -0.092 -0.055 -0.174 0.396
Kfs … 0.141 0.309 1 -0.158 0.102 -0.100 -0.061 -0.103 0.140 -0.236 0.032 -0.116
Cal … -0.403 -0.188 -0.158 1 0.034 -0.146 -0.104 -0.029 -0.333 0.493 0.269 0.278
Dol … -0.308 0.011 0.102 0.034 1 0.199 -0.076 -0.091 0.085 -0.032 0.152 -0.085
SSA … -0.716 -0.385 -0.100 -0.146 0.199 1 -0.065 -0.084 0.450 -0.020 0.111 -0.093
Zn … 0.166 -0.120 -0.061 -0.104 -0.076 -0.065 1 0.917 0.397 0.111 0.065 -0.142
Cd … 0.123 -0.006 -0.103 -0.029 -0.091 -0.084 0.917 1 0.311 0.207 0.001 0.134
Pb … -0.201 -0.092 0.140 -0.333 0.085 0.450 0.397 0.311 1 0.023 0.176 -0.174
Cr … -0.334 -0.055 -0.236 0.493 -0.032 -0.020 0.111 0.207 0.023 1 0.332 0.311
Cu … -0.274 -0.174 0.032 0.269 0.152 0.111 0.065 0.001 0.176 0.332 1 -0.157
Fe … -0.157 0.396 -0.116 0.278 -0.085 -0.093 -0.142 0.134 -0.174 0.311 -0.157 1
(1 out of 3)
Table V.2. Correlation matrix of the 34 variables (sig. unilateral)
When correlation coefficient is < 0.05, then it is significant.
pH Eh EC WSOC WSIC h Sol_NH4 Sol_Na Sol_K Sol_Ca Sol_Mg Sol_Cl 

pH 0 0.001 0.227 0 0.272 0.001 0.008 0.008 0.147 0.002 0.027 …
Eh 0 0 0 0 0.150 0 0 0 0.438 0.030 0.001 …
EC 0.001 0 0.033 0 0.158 0.147 0 0.008 0.125 0 0 …
WSOC 0.227 0 0.033 0.025 0.185 0 0.250 0 0.124 0.396 0.370 …
WSIC 0 0 0 0.025 0.005 0 0 0 0.249 0 0 …
h 0.272 0.150 0.158 0.185 0.005 0.058 0.190 0.083 0.142 0 0.276 …
Sol_NH4+ 0.001 0 0.147 0 0 0.058 0.473 0 0.094 0.019 0.066 …
Sol_Na+ 0.008 0 0 0.250 0 0.190 0.473 0.078 0.243 0 0 …
Sol_K+ 0.008 0 0.008 0 0 0.083 0 0.078 0.071 0.035 0.487 …
Sol_Ca2+ 0.147 0.438 0.125 0.124 0.249 0.142 0.094 0.243 0.071 0.014 0.183 …
Sol_Mg2+ 0.002 0.030 0 0.396 0 0 0.019 0 0.035 0.014 0 …
Sol_Cl- 0.027 0.001 0 0.370 0 0.276 0.066 0 0.487 0.183 0 …
Alk 0 0 0.031 0 0 0.030 0 0.250 0 0.100 0.138 0.221 …
Sol_SO42- 0.001 0.262 0 0.011 0 0.228 0.046 0 0.134 0 0.009 0 …
Sol_F- 0.044 0.028 0 0.248 0 0.274 0.046 0 0.416 0.192 0 0 …
Ex_NH4+ 0.002 0 0.236 0 0 0.025 0 0.339 0 0.043 0.020 0.035 …
Ex_Na+ 0.001 0 0 0.091 0 0.084 0.091 0 0.008 0.431 0.004 0 …
Ex_K+ 0 0 0.004 0 0 0.005 0 0.059 0 0.063 0.228 0.415 …
Ex_Ca2+ 0 0.004 0 0.105 0 0.214 0.347 0 0.180 0.057 0.001 0 …
Ex_Mg2+ 0 0.132 0.388 0.005 0.029 0 0.199 0.379 0.032 0.422 0 0.440 …
CEC 0.009 0.066 0.180 0.083 0.018 0 0.002 0.311 0.004 0.059 0.051 0.456 …
Sheet silicates 0.004 0.335 0.264 0.153 0.071 0 0.174 0.216 0.346 0.091 0 0.185 …
Qtz 0 0.019 0.010 0.272 0 0 0.002 0.019 0.007 0.032 0 0.057 …
Nfs 0.016 0.002 0.431 0 0.472 0 0.006 0.377 0.002 0.328 0.254 0.161 …
Kfs 0.001 0.008 0.328 0.083 0.165 0.017 0.218 0.293 0.289 0.364 0.003 0.202 …
Cal 0 0 0 0.005 0 0.471 0.001 0 0 0.141 0.226 0 …
Dol 0 0.277 0.405 0.043 0.244 0.464 0.428 0.294 0.163 0.337 0.276 0.346 …
SSA 0 0.298 0.050 0.026 0.236 0 0.270 0.036 0.362 0.244 0 0.039 …
Zn 0.084 0.067 0.474 0.131 0.329 0.254 0.060 0.299 0.059 0 0.483 0.396 …
Cd 0.266 0.415 0.491 0.421 0.465 0.362 0.349 0.234 0.416 0 0.283 0.214 …
Pb 0.040 0.317 0.143 0.261 0.260 0 0.124 0.085 0.222 0 0.028 0.072 …
Cr 0.153 0.082 0 0.002 0 0.028 0.006 0 0.001 0.234 0.098 0 …
Cu 0.012 0.353 0 0.003 0 0.003 0.029 0 0.076 0.011 0 0 …
Fe 0.037 0.001 0.291 0 0.111 0.426 0 0.378 0 0.165 0.085 0.072 …
Table V.2. Correlation matrix of the 34 variables (sig. unilateral) (2 out of 3)

Sheet
 Alk Sol_SO42- Sol_F- Ex_NH4+Ex_Na+ Ex_K+Ex_Ca2+ Ex_Mg2+ CEC 
silicates
pH … 0 0.001 0.044 0.002 0.001 0 0 0 0.009 0.004 …
Eh … 0 0.262 0.028 0 0 0 0.004 0.132 0.066 0.335 …
EC … 0.031 0 0 0.236 0 0.004 0 0.388 0.180 0.264 …
WSOC … 0 0.011 0.248 0 0.091 0 0.105 0.005 0.083 0.153 …
WSIC … 0 0 0 0 0 0 0 0.029 0.018 0.071 …
h … 0.030 0.228 0.274 0.025 0.084 0.005 0.214 0 0 0 …
Sol_NH4+ … 0 0.046 0.046 0 0.091 0 0.347 0.199 0.002 0.174 …
Sol_Na+ … 0.250 0 0 0.339 0 0.059 0 0.379 0.311 0.216 …
Sol_K+ … 0 0.134 0.416 0 0.008 0 0.180 0.032 0.004 0.346 …
Sol_Ca2+ … 0.100 0 0.192 0.043 0.431 0.063 0.057 0.422 0.059 0.091 …
Sol_Mg2+ … 0.138 0.009 0 0.020 0.004 0.228 0.001 0 0.051 0 …
Sol_Cl- … 0.221 0 0 0.035 0 0.415 0 0.440 0.456 0.185 …
Alk … 0.052 0.134 0 0.020 0 0.358 0.494 0 0.043 …
Sol_SO42- … 0.052 0 0.014 0 0.253 0.033 0.265 0.066 0.485 …
Sol_F- … 0.134 0 0.025 0 0.415 0 0.467 0.446 0.268 …
Ex_NH4+ … 0 0.014 0.025 0.083 0 0.319 0.371 0 0.067 …
Ex_Na+ … 0.020 0 0 0.083 0 0 0.390 0.058 0.224 …
Ex_K+ … 0 0.253 0.415 0 0 0.263 0.153 0 0.001 …
Ex_Ca2+ … 0.358 0.033 0 0.319 0 0.263 0 0.001 0 …
Ex_Mg2+ … 0.494 0.265 0.467 0.371 0.390 0.153 0 0 0 …
CEC … 0 0.066 0.446 0 0.058 0 0.001 0 0 …
Sheet silicates … 0.043 0.485 0.268 0.067 0.224 0.001 0 0 0 …
Qtz … 0 0.333 0.029 0 0 0 0 0 0 0 …
Nfs … 0.002 0.183 0.119 0.048 0.135 0.005 0.062 0.001 0.105 0 …
Kfs … 0.234 0.120 0.467 0.102 0.325 0.262 0.470 0.261 0.011 0.005 …
Cal … 0 0.266 0 0 0 0 0 0.221 0.014 0.347 …
Dol … 0.464 0.017 0.311 0.414 0.258 0.392 0 0 0.137 0.002 …
SSA … 0.095 0.446 0.046 0.068 0.283 0.007 0.009 0 0 0 …
Zn … 0.060 0.414 0.422 0.055 0.190 0.050 0.421 0.163 0.187 0.159 …
Cd … 0.283 0.312 0.248 0.364 0.223 0.480 0.355 0.158 0.293 0.135 …
Pb … 0.159 0.199 0.062 0.237 0.118 0.103 0.216 0 0.003 0 …
Cr … 0.001 0 0 0.004 0 0 0 0.108 0.002 0.062 …
Cu … 0.048 0 0 0.009 0 0.150 0 0.001 0.123 0.027 …
Fe … 0 0.017 0.094 0 0.279 0 0.213 0.487 0 0.358 …
Table V.2. Correlation matrix of the 34 variables (sig. unilateral) (3 out of 3)
 Qtz Nfs Kfs Cal Dol SSA Zn Cd Pb Cr Cu Fe

pH … 0 0.016 0.001 0 0 0 0.084 0.266 0.040 0.153 0.012 0.037
Eh … 0.019 0.002 0.008 0 0.277 0.298 0.067 0.415 0.317 0.082 0.353 0.001
EC … 0.010 0.431 0.328 0 0.405 0.050 0.474 0.491 0.143 0 0 0.291
WSOC … 0.272 0 0.083 0.005 0.043 0.026 0.131 0.421 0.261 0.002 0.003 0
WSIC … 0 0.472 0.165 0 0.244 0.236 0.329 0.465 0.260 0 0 0.111
h … 0 0 0.017 0.471 0.464 0 0.254 0.362 0 0.028 0.003 0.426
Sol_NH4+ … 0.002 0.006 0.218 0.001 0.428 0.270 0.060 0.349 0.124 0.006 0.029 0
Sol_Na+ … 0.019 0.377 0.293 0 0.294 0.036 0.299 0.234 0.085 0 0 0.378
Sol_K+ … 0.007 0.002 0.289 0 0.163 0.362 0.059 0.416 0.222 0.001 0.076 0
Sol_Ca2+ … 0.032 0.328 0.364 0.141 0.337 0.244 0 0 0 0.234 0.011 0.165
Sol_Mg2+ … 0 0.254 0.003 0.226 0.276 0 0.483 0.283 0.028 0.098 0 0.085
Sol_Cl- … 0.057 0.161 0.202 0 0.346 0.039 0.396 0.214 0.072 0 0 0.072
Alk … 0 0.002 0.234 0 0.464 0.095 0.060 0.283 0.159 0.001 0.048 0
Sol_SO42- … 0.333 0.183 0.120 0.266 0.017 0.446 0.414 0.312 0.199 0 0 0.017
Sol_F- … 0.029 0.119 0.467 0 0.311 0.046 0.422 0.248 0.062 0 0 0.094
Ex_NH4+ … 0 0.048 0.102 0 0.414 0.068 0.055 0.364 0.237 0.004 0.009 0
Ex_Na+ … 0 0.135 0.325 0 0.258 0.283 0.190 0.223 0.118 0 0 0.279
Ex_K+ … 0 0.005 0.262 0 0.392 0.007 0.050 0.480 0.103 0 0.150 0
Ex_Ca2+ … 0 0.062 0.470 0 0 0.009 0.421 0.355 0.216 0 0 0.213
Ex_Mg2+ … 0 0.001 0.261 0.221 0 0 0.163 0.158 0 0.108 0.001 0.487
CEC … 0 0.105 0.011 0.014 0.137 0 0.187 0.293 0.003 0.002 0.123 0
Sheet silicates … 0 0 0.005 0.347 0.002 0 0.159 0.135 0 0.062 0.027 0.358
Qtz … 0.002 0.053 0 0 0 0.028 0.079 0.010 0 0.001 0.035
Nfs … 0.002 0 0.015 0.450 0 0.085 0.473 0.145 0.265 0.022 0
Kfs … 0.053 0 0.035 0.121 0.127 0.243 0.118 0.055 0.003 0.357 0.091
Cal … 0 0.015 0.035 0.349 0.047 0.117 0.372 0 0 0.001 0.001
Dol … 0 0.450 0.121 0.349 0.011 0.191 0.148 0.165 0.359 0.041 0.164
SSA … 0 0 0.127 0.047 0.011 0.227 0.168 0 0.410 0.102 0.143
Zn … 0.028 0.085 0.243 0.117 0.191 0.227 0 0 0.102 0.230 0.052
Cd … 0.079 0.473 0.118 0.372 0.148 0.168 0 0 0.008 0.496 0.061
Pb … 0.010 0.145 0.055 0 0.165 0 0 0 0.394 0.021 0.022
Cr … 0 0.265 0.003 0 0.359 0.410 0.102 0.008 0.394 0 0
Cu … 0.001 0.022 0.357 0.001 0.041 0.102 0.230 0.496 0.021 0 0.035
Fe … 0.035 0 0.091 0.001 0.164 0.143 0.052 0.061 0.022 0 0.035
Table V.3. Loadings of the 34 variables on the seven significant PC calculated by PCA
PC
1 2 3 4 5 6 7
pH -0.021 0.032 -0.013 0.024 0.293 0.183 -0.019
Eh -0.012 -0.077 0.016 -0.008 -0.082 -0.220 -0.004
EC 0.143 0.008 -0.012 0.002 -0.059 0.045 0.003
WSOC 0.010 0.103 -0.014 0.000 -0.110 0.038 0.079
WSIC 0.108 0.060 0.011 0.003 -0.017 -0.032 -0.114
h 0.026 0.021 0.192 0.019 -0.202 0.002 -0.059
Sol_NH4+ -0.020 0.175 -0.014 0.007 0.012 -0.031 -0.104
Sol_Na+ 0.149 -0.012 -0.006 -0.023 -0.080 0.047 0.008
Sol_K+ 0.005 0.172 -0.014 -0.004 -0.046 -0.017 -0.107
Sol_Ca2+ 0.005 0.000 -0.018 0.294 0.052 0.052 -0.038
Sol_Mg2+ 0.065 -0.081 0.156 0.004 -0.186 0.308 0.167
Sol_Cl- 0.148 -0.032 -0.007 -0.025 -0.073 0.047 0.006
Alk -0.013 0.159 0.005 0.011 0.007 0.007 -0.035
Sol_SO42- 0.056 0.038 -0.050 0.023 0.138 -0.039 -0.365
Sol_F- 0.146 -0.035 -0.007 -0.023 -0.062 0.000 0.009
Ex_NH4+ -0.023 0.167 -0.004 -0.001 0.019 -0.067 -0.080
Ex_Na+ 0.130 0.022 -0.022 -0.028 0.015 -0.067 -0.056
Ex_K+ 0.000 0.159 0.022 -0.010 0.002 -0.017 -0.102
Ex_Ca2+ 0.015 -0.066 -0.018 0.052 0.331 -0.035 0.197
Ex_Mg2+ -0.020 -0.054 0.178 -0.007 0.051 0.076 0.092
CEC 0.002 -0.018 0.136 0.014 -0.065 0.005 0.289
Sheet silicates -0.019 -0.003 0.182 -0.037 0.008 -0.076 -0.020
Qtz -0.006 -0.004 -0.129 0.044 -0.099 0.067 -0.072
Nfs -0.019 0.009 -0.049 0.011 -0.039 0.332 0.207
Kfs -0.012 -0.010 -0.009 -0.018 0.004 0.373 -0.055
Cal 0.066 0.009 -0.069 -0.017 0.159 -0.171 0.154
Dol -0.057 0.009 -0.064 -0.006 0.424 -0.078 -0.161
SSA -0.033 0.002 0.197 -0.028 -0.023 0.005 -0.069
Zn -0.004 -0.001 -0.016 0.340 0.017 -0.058 0.012
Cd -0.011 0.005 -0.020 0.346 0.023 -0.041 0.136
Pb -0.022 0.058 0.123 0.153 -0.095 0.098 -0.223
Cr 0.094 0.018 0.003 0.074 -0.013 -0.142 0.110
Cu 0.091 -0.041 0.046 0.030 -0.001 0.021 -0.049
Fe -0.012 0.007 0.002 0.042 -0.019 0.078 0.434
Table V.4. Scores of the 133 landfill samples on the seven significant PC rotated according to the Varimax
method
SAMPLE PC 1 PC 2 PC 3 PC 4 PC 5 PC 6 PC 7
Z4V1S1M01 4.246 -0.377 0.138 0.120 -0.386 -0.518 -0.260
Z4V1S1M02 3.512 -0.185 -0.205 -0.260 -0.029 -0.776 -0.383
Z4V1S1M03 3.386 -0.148 -0.200 -0.197 -0.163 -0.702 -0.137
Z4V1S1M04 3.274 -0.115 -0.271 -0.396 0.141 -0.837 -0.513
Z4V1S1M05 5.667 -0.848 1.182 0.456 -1.507 1.396 -0.043
Z4V1S1M06 3.962 0.108 -0.228 -0.108 0.548 -0.935 -1.235
Z4V1S1M07 2.193 -0.145 -0.149 0.139 2.234 -1.453 -0.861
Z4V1S1M08 0.716 -0.648 0.285 -0.285 1.410 -0.536 -0.313
Z4V1S1M09 -0.291 -0.736 -0.077 -0.277 3.145 -0.684 0.267
Z4V1S1M10 -0.165 -0.725 0.360 -0.241 2.387 -0.728 0.556
Z4V1S2M01 1.614 -0.204 -0.876 -0.303 -0.083 0.581 0.502
Z4V1S2M02 1.453 -0.331 -0.826 -0.336 -0.291 1.223 0.387
Z4V1S2M03 1.371 -0.378 -0.808 -0.247 -0.324 1.306 0.558
Z4V1S2M04 1.354 -0.788 0.023 -0.340 -1.117 4.045 1.205
Z4V1S2M05 0.956 -0.267 -0.940 -0.349 -0.043 0.960 0.543
Z4V1S2M06 1.106 -0.437 -0.873 -0.137 0.418 0.907 0.853
Z4V1S2M07 0.448 -0.627 -0.799 -0.250 0.205 0.731 0.710
Z4V1S2M08 -0.024 -0.967 0.704 -0.112 1.116 -0.723 1.384
Z4V1S2M09 0.022 -1.079 0.462 -0.054 0.994 -0.891 1.493
Z4V1S2M10 -0.199 -0.726 -0.507 -0.188 1.298 -0.081 1.093
Z4V1S2M11 -0.316 -0.671 -1.115 -0.248 1.259 0.322 0.823
Z4V1S3M01 0.031 -0.920 -0.027 0.230 1.703 -1.041 -0.319
Z4V1S3M02 -0.324 -0.979 0.106 -0.092 1.782 -0.765 0.699
Z4V1S3M03 -0.379 -1.009 0.166 -0.180 1.720 -0.779 0.855
Z4V1S3M04 -0.348 -0.965 0.157 -0.234 1.472 -0.718 0.831
Z4V1S3M05 -0.310 -0.857 -0.257 -0.178 1.753 -0.754 0.809
Z4V1S3M06 -0.302 -0.828 -0.445 -0.227 1.789 -0.534 0.647
Z4V1S3M07 -0.490 -0.876 -1.167 -0.271 2.200 -0.248 0.119
Z4V1S3M08 -0.359 -1.040 -0.026 -0.206 1.798 -0.338 1.005
Z4V1S3M09 -0.443 -0.833 -0.537 -0.253 2.742 -0.695 0.370
Z6V1S1M01 0.016 1.215 0.533 0.313 -0.423 0.543 -1.031
Z6V1S1M02 -0.282 0.625 0.294 -0.224 -0.090 0.294 -0.729
Z6V1S1M03 -0.283 0.467 0.590 -0.216 -0.107 0.151 -0.715
Z6V1S1M04 -0.247 0.436 0.535 -0.252 -0.015 0.095 -0.680
Z6V1S1M05 -0.228 0.180 0.704 -0.229 0.054 0.076 -0.670
Z6V1S1M06 -0.158 0.134 0.733 -0.160 0.141 0.242 -0.847
Z6V1S1M07 -0.210 -0.323 0.293 -0.307 0.004 0.494 -0.750
Z6V1S1M08 -0.149 -0.361 -0.007 -0.026 -0.089 0.689 -0.670
Z6V1S1M09 -0.189 -0.375 -0.090 0.393 -0.040 0.507 -0.848
… … … … … … … …
↓ ↓
↑ ↑
… … … … … … … …
Z6V1S1M10 -0.218 -0.582 -0.526 0.305 -0.003 0.795 -0.802
Z6V1S1M11 -0.218 -0.551 -0.737 0.117 -0.105 1.293 -0.891
Z6V1S1M12 -0.218 -0.378 -0.759 1.027 0.198 1.135 -0.835
Z6V1S1M13 -0.218 -0.332 1.121 0.003 0.332 -0.010 -0.941
Z6V1S1M14 -0.218 -0.637 -0.388 -0.202 0.420 2.127 -1.062
Z6V1S2M01 -0.218 1.589 -0.351 -0.086 1.584 1.041 -1.658
Z6V1S2M02 -0.218 1.268 -0.117 1.620 1.056 0.594 -2.006
Z6V1S2M03 -0.218 0.954 0.097 -0.044 0.635 0.096 -1.697
Z6V1S2M04 -0.218 0.613 -0.139 -0.087 0.675 0.571 -1.578
Z6V1S2M05 -0.218 0.458 -0.340 -0.171 0.576 -0.071 -1.556
Z6V1S2M06 -0.218 0.863 -0.188 -0.012 0.099 0.598 -1.245
Z6V1S2M07 -0.218 0.209 -0.676 -0.276 0.883 0.284 -1.149
Z6V1S2M08 -0.218 -0.315 -0.373 0.041 1.546 0.120 -1.636
Z6V1S2M09 -0.218 -0.484 0.398 -0.213 0.725 0.705 -1.007
Z6V1S2M10 -0.218 -0.405 -0.927 0.152 0.503 0.784 -1.491
Z6V1S2M11 -0.218 -0.423 -0.554 0.112 0.934 0.497 -1.198
Z6V1S2M12 -0.218 -0.463 -0.454 0.273 0.076 1.176 -1.553
Z6V2S1M01 -0.218 1.776 1.732 1.058 -0.470 0.317 -0.692
Z6V2S1M02 -0.218 1.742 1.741 0.035 0.066 -0.374 -1.048
Z6V2S1M03 -0.218 1.280 1.374 -0.139 0.771 -0.445 -0.991
Z6V2S1M04 -0.218 1.045 1.496 -0.134 0.833 -0.428 -0.858
Z6V2S1M05 -0.218 0.932 1.421 -0.117 0.833 -0.448 -0.521
Z6V2S1M06 -0.218 0.787 1.941 -0.168 0.330 -0.324 -0.427
Z6V2S1M07 -0.218 0.568 2.074 -0.265 0.112 -0.297 -0.129
Z6V2S1M08 -0.218 0.045 2.005 -0.259 0.307 -0.124 -0.067
Z6V2S1M09 -0.218 -0.388 2.380 -0.211 -0.282 -0.090 0.339
Z6V2S1M10 -0.218 -0.613 2.336 -0.272 0.122 0.019 0.339
Z6V2S1M11 -0.218 -0.657 2.422 -0.209 0.140 0.138 0.188
Z6V2S1M12 -0.218 -0.799 1.242 -0.164 0.774 -0.286 0.452
Z6V2S1M13 -0.218 -0.653 1.723 -0.378 -0.686 0.268 0.411
Z6V2S2M01 -0.218 1.174 -0.490 0.021 -0.024 1.266 -1.012
Z6V2S2M02 -0.218 1.064 -0.568 -0.170 -0.124 1.327 -0.644
Z6V2S2M03 -0.218 0.589 -0.173 -0.052 -0.165 1.385 -0.865
Z6V2S2M04 -0.218 -0.151 1.402 0.172 -0.570 1.517 0.520
Z6V2S2M05 -0.218 -0.387 2.597 0.174 -0.875 0.267 0.650
Z6V2S2M06 -0.218 -0.503 2.262 0.114 -0.604 0.084 0.306
Z6V2S2M07 -0.218 -0.517 2.667 0.138 -1.057 0.210 0.467
Z6V2S2M08 -0.218 -0.547 2.634 0.139 -1.101 0.145 0.402
Z6V2S2M09 -0.320 -0.611 2.710 0.143 -1.294 0.176 0.593
Z6V2S2M10 -0.276 -0.692 2.407 0.360 -0.710 0.113 0.273
… … … … … … …
↓ ↓
↑ ↑
… … … … … … … …
Z6V2S2M11 -0.592 -0.579 -0.115 -0.125 0.016 2.080 -0.543
Z6V2S2M12 -0.653 -0.466 0.220 -0.267 0.413 1.634 -0.352
Z6V2S2M13 -0.500 -0.478 -0.156 -0.265 -0.324 1.380 -0.483
Z6V2S2M14 -0.586 -0.520 -0.602 -0.251 -0.239 2.193 -0.049
Z1V1S1M01 -0.502 -0.584 -0.708 -0.381 -1.499 -0.984 -0.333
Z1V1S1M02 -0.511 -0.652 -0.575 -0.473 -1.419 -1.101 -0.140
Z1V1S1M03 -0.456 -0.677 -0.489 -0.460 -1.509 -1.378 -0.248
Z1V1S1M04 -0.452 -0.767 -0.420 -0.373 -1.513 -1.346 -0.220
Z1V1S1M05 -0.437 -0.795 -0.370 -0.234 -1.475 -1.400 -0.386
Z1V1S1M06 -0.422 -0.509 -0.687 -0.343 -1.513 -1.058 -0.254
Z1V1S1M07 -0.486 -0.536 -0.799 -0.470 -1.382 -1.145 -0.316
Z1V1S1M08 -0.314 -0.897 -0.732 -0.327 -1.199 -0.194 -0.511
Z1V1S1M09 -0.384 -0.867 -0.836 -0.380 -1.194 -0.854 -0.340
Z1V1S1M10 -0.393 -0.515 -0.588 -0.339 -1.551 -0.956 -0.219
Z1V1S1M11 -0.478 -1.050 -0.668 -0.430 -1.520 -1.706 -0.236
Z1V1S1M12 -0.401 -0.995 -0.360 -0.453 -1.576 -1.547 -0.146
Z1V1S1M13 -0.418 -0.990 -0.112 -0.517 -1.434 -1.904 0.148
Z1V1S1M14 -0.518 -0.927 -0.814 -0.492 -1.130 -1.337 -0.015
Z1V1S1M15 -0.529 -0.740 -0.880 -0.449 -0.997 -1.283 0.068
Z1V1S2M01 -0.160 -0.260 -0.721 10.436 -0.081 -0.928 0.415
Z1V1S2M02 -0.427 -0.575 -0.697 2.807 -0.612 -0.255 -0.724
Z1V1S2M03 -0.456 -0.557 -0.738 0.218 -0.921 -0.617 -0.278
Z1V1S2M04 -0.444 -0.524 -0.604 -0.130 -0.921 -0.537 -0.315
Z1V1S2M05 -0.399 -0.401 -0.280 -0.044 -1.161 -0.646 -0.290
Z1V1S2M06 -0.330 -0.548 -0.185 0.367 -1.371 -0.391 -0.091
Z1V1S2M07 -0.368 -0.595 -0.305 0.070 -1.213 -0.817 -0.369
Z1V1S2M08 -0.348 -0.643 -0.405 0.413 -1.207 -0.471 -0.414
Z1V1S2M09 -0.437 -0.653 -0.799 -0.312 -1.034 -0.673 -0.308
Z1V1S2M10 -0.406 -0.703 -0.674 0.052 -0.831 -0.439 -0.340
Z1V1S2M11 -0.646 -0.664 -1.584 -0.544 -0.425 -0.092 -0.257
Z1V1S2M12 -0.679 -0.577 -1.572 -0.468 -0.131 0.456 -0.024
Z1V1S2M13 -0.652 -0.569 -1.539 -0.410 0.086 0.284 -0.077
Z5V1S1M01 0.002 1.732 -0.367 0.280 -0.394 0.380 -0.936
Z5V1S1M02 -0.277 0.715 -1.465 -0.367 -0.264 -0.210 -0.466
Z5V1S1M03 -0.320 1.971 -0.846 -0.555 -0.234 0.437 -0.081
Z5V1S1M04 -0.068 2.380 -0.678 -0.453 -0.322 -0.443 -0.409
Z5V1S1M05 -0.443 1.034 -1.279 -0.523 0.013 0.666 -0.322
Z5V1S1M06 -0.134 -0.173 -0.761 -0.262 -1.589 0.964 1.734
Z5V1S2M01 -0.168 1.641 -0.949 0.139 -0.416 0.375 1.301
Z5V1S2M02 0.118 2.923 -0.275 -0.216 -0.300 -1.307 0.573
… … … … … … …
↓ ↓
↑ ↑
… … … … … … … …
Z5V1S2M03 0.238 2.497 -0.514 -0.417 0.115 -1.555 0.695
Z5V1S2M04 0.188 2.652 -0.411 -0.411 -0.035 -1.313 0.484
Z5V1S2M05 0.220 1.991 -0.212 -0.473 0.196 -1.390 1.032
Z5V1S2M06 0.304 1.767 -0.325 -0.471 0.331 -1.474 0.915
Z5V1S2M07 -0.133 -0.193 -0.312 -0.157 -0.083 3.269 2.764
Z5V1S3M01 -0.139 3.030 -0.457 0.174 -0.974 0.496 0.699
Z5V1S3M02 -0.233 2.178 -0.366 0.013 -0.867 0.691 2.456
Z5V1S3M03 -0.334 1.908 -0.395 0.224 -0.353 0.065 1.935
Z5V1S3M04 -0.304 1.878 -0.826 0.033 -0.101 1.044 2.172
Z5V1S3M05 0.303 2.014 0.487 0.155 0.106 -1.397 2.638
Z5V1S3M06 0.194 1.233 -0.047 0.042 0.936 -1.411 1.825
Z5V1S3M07 -0.284 0.034 -0.688 -0.007 0.279 1.086 2.501
Z5V1S3M08 -0.351 -0.849 -0.312 0.624 0.543 0.537 3.130
Z5V1S3M09 -0.352 -0.820 -0.469 0.556 0.215 0.548 2.921
APPENDIX VI. BAILÉN CLAY DATA FROM THE FOUR-YEAR EXPERIMENT
Table VI.1 Heights, thicknesses and depths of Bailén (A2) samples ............................................................................................................................. A-81
Table VI.2 pH, redox potential, electrical conductivity, water soluble organic/inorganic carbon, moisture of A2 samples ......................................... A-82
Table VI.3 Soluble ions (mmol/kg) in aqueous extracts of A2 samples ........................................................................................................................ A-83
Table VI.4 Heavy metals (µg/g) and iron (mg/g) of A2 samples................................................................................................................................... A-84
Table VI.5 Exchangeable cations and cationic-exchange capacities [cmol(+)/kg] of A2 samples ................................................................................ A-85
Table VI.6 Semi-quantitative average mineralogical composition (mass %, DRX) and specific surface (Se: m2/g) of A2 samples ............................ A-86
Fig. VI.1 X-ray powder-diffraction patterns (a.u: arbitrary units) of A2L1................................................................................................................... A-87
Fig. VI.5 X-ray diffraction patterns of oriented slides of A2L1M5. .............................................................................................................................. A-89
Fig. VI.6 X-ray diffraction patterns of oriented slides of A2L2M04. ............................................................................................................................ A-89
Fig. VI.7 X-ray diffraction patterns of oriented slides of A2L3M01crust. .................................................................................................................... A-90
Fig. VI.8 X-ray diffraction patterns of oriented slides of A2L3M01 ............................................................................................................................. A-90
Fig. VI.9 X-ray diffraction patterns of oriented slides of A2L3M02 ............................................................................................................................. A-91
Fig. VI.10 X-ray diffraction patterns of oriented slides of A2L3M03. .......................................................................................................................... A-91
Fig. VI.11 X-ray diffraction patterns of oriented slides of A2L4M01 ........................................................................................................................... A-92
Fig. VI.14 X-ray diffraction patterns of oriented slides of A2L4M5.1. ......................................................................................................................... A-93
A-79 Regadío, M. 2012. Diffusion of pollutants in old landfills built over clayey substrata. PhD Thesis BAILÉN DATA. APPENDIX VI
Fig. VI.15 X-ray diffraction patterns of oriented slides of A2L4M5.2. ......................................................................................................................... A-94
Fig. VI.16 X-ray diffraction patterns (a.u: arbitrary units) of oriented slides of A2L3 and A2L4, compared with the original clay A2. ..................... A-94
Fig. VI.17 FTIR spectra of the original A2 and the A2L3M01crust. ............................................................................................................................. A-95
Fig. VI.18 FTIR spectra of the original A2 and the A2L3M01. .................................................................................................................................... A-95
Conversion to SI units:
equivalence
Lengh: 1 cm 10-2 m
equivalence
Electrical conductivity: 1 mS/cm 102 mS/m
Table VI.1 Heights, thicknesses and depths of Bailén (A2) samples
A2L1 A2L2
a Average
Minimum & maximum heights Thickness Minimum & maximum heightsa Thickness Average depthb
Sample depthb Sample
(m) (cm) (m) (cm) (m)
(m)
M01 0.54 IF 0 M01 0.52 IF 0
M02 0.54-0.51 3.5 0.0175 M02 0.52-0.49.5 2.5 0.0125
M03 0.51-0.45 5.5 0.0625 M03 0.49.5-0.47 2.5 0.0375
M5 0.45-0.40 5 0.115 M04 0.47-0.40 7 0.085
M5 0.40-0.33 7 0.155
M4 0.33-0.24 9 0.235
M3 0.24-0.14 10 0.33
M2 0.14-0.04 10 0.43
M1 0.04-0 4 0.51
A2L3 A2L4
a Average
Minimum & maximum heights Thickness Minimum & maximum heightsa Thickness Average depthb
Sample depthb Sample
(m) (cm) (m) (cm) (m)
(m)
M01 0.54 IF 0 M01 55 IF 0
M02 0.54-0.515 2.5 0.0125 M02 0.55-0.525 2.5 0.0125
M03 0.51.5-0.49 2.5 0.0375 M03 0.525-0.50 2.5 0.0375
M04 0.49-0.465 2.5 0.0625 M5.1 0.50-0.45 5 0.075
M05 0.46.5-0.44 2.5 0.0875 M5.2 0.45-0.40 5 0.125
M06 0.44-0.42 2 0.11 M4 0.40-0.26 14 0.22
M6 0.42-0.32 10 0.17 M3 0.26-0.16 10 0.34
M5 0.32-0.26 6 0.25 M2 0.16-0.06 10 0.44
M4 0.26-0.20 6 0.31 M1 0.06-0 6 0.52
M3 0.20-0.15 5 0.365
M2 0.15-0.075 7.5 0.4275
M1 0.07.5-0 7.5 0.5025
a
Heights measured from the bottom, bAverage depth measured from the clay surface, IF: top area of the clay in contact with the leachate.
Table VI.2 pH, redox potential (Eh: mv), electrical conductivity (EC: mS/cm), water soluble organic/inorganic carbon (WSOC/WSIC: µg/g), moisture (h: %) of Bailén
samples
A2L1 A2L2
Sample Sample
M01 7.3 n.d. 0.4 64 90 28.66 M01 7.5 n.d. 0.4 66 108 53.09
M02 8 203 0.6 59 97 24.34 M02 7.6 198 2.2 48 83 32.96
M03 7.9 178 1.1 49 83 25.92 M03 7.8 186 1.6 64 98 30.49
M5 7.6 204 2.6 55 69 25.38 M04 7.7 187 3.1 59 100 31.22
M5 7.6 186 3.2 77 101 25.70
M4 7.6 189 3.2 75 99 24.72
M3 7.6 189 3.2 77 89 22.72
M2 7.6 185 3.3 85 93 23.70
M1 7.7 184 3.3 98 96.6 24.14
A2L3 A2L4
Sample Sample
M01 7.42 n.d. 1.0 83 134 50.40 M01 8.1 170 6.7 649 202 36.90
M02 8 140 2.7 61 111 37.95 M02 8.9 135 3.6 473 556 39.17
M03 8 149 2.7 55 101 33.44 M03 8.9 101 3.3 627 383 39.24
M04 7.8 209 2.4 58 116 32.25 M5.1 8 131 6.8 416 329 36.67
M05 7.9 198 3 61 164 29.79 M5.2 8.3 118 5.4 514 168 27.76
M06 7.7 200 4.1 65 115 26.57 M4 8.4 111 4 544 277 1.49
M6 7.6 214 4 70 88 20.63 M3 7.8 137 5.6 354 91 1.77
M5 7.6 188 3.8 77 81 23.03 M2 7.8 133 5.2 311 72 2.11
M4 7.6 187 3.6 80 87 20.09 M1 7.7 128 4.8 282 77 2.16
M3 7.6 195 3.7 86 85 21.51
M2 7.5 199 3.7 79 91 23.01
M1 7.6 197 3.6 77 101 22.98
n.d.: no detected.
Table VI.3 Soluble ions (mmol/kg) in aqueous extracts of Bailén samples
A2L1 A2L2
Sample Soluble cations Soluble anions Sample Soluble cations Soluble anions
NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk SO42- NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk SO42-
M01 <0.15 0.08 0.10 1.88 0.76 1.18 50.82 32.69 M01 <0.21 0.28 0.43 1.39 0.63 19.58 1.24 16.24
M02 0.01 <0.04 0.07 0.85 0.28 1.41 7.87 10.31 M02 0.01 0.24 0.55 3.25 1.19 8.43 14.62 55.28
M03 0.01 <0.04 0.09 1.88 0.54 1.55 6.67 27.90 M03 0.01 0.20 0.43 1.76 0.77 8.35 12.52 23.94
M5 0.01 0.11 0.14 2.37 0.46 n.d. 7.81 116.59 M04 0.01 0.24 0.78 7.51 1.61 9.36 16.58 109.30
M5 0.06 0.23 0.65 6.70 1.73 5.70 14.83 88.59
M4 0.11 0.23 0.55 8.09 2.11 5.11 14.12 105.24
M3 0.11 0.26 0.58 8.88 2.63 5.02 12.06 120.34
M2 0.10 0.37 0.51 8.71 2.64 4.91 11.88 122.52
M1 0.16 0.90 0.66 10.02 3.23 7.45 10.52 102.95
A2L3 A2L4
Sample Soluble cations Soluble anions Sample Soluble cations Soluble anions
NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk SO42- NH4+ Na+ K+ Ca2+ Mg2+ Cl- Alk SO42-
M01 55.22 1.83 0.90 2.24 1.12 24.14 31.26 35.60 M01 132.85 7.11 2.50 0.63 0.48 53.03 144.19 60.58
M02 31.47 1.41 0.83 2.51 0.79 16.56 15.84 42.68 M02 96.04 4.83 1.87 0.09 0.04 42.87 162.80 14.57
M03 28.26 1.44 0.90 2.85 1.74 15.82 14.63 50.80 M03 66.43 4.91 1.76 0.35 0.06 34.41 143.57 12.70
M04 28.57 1.17 0.81 4.70 1.48 15.60 14.62 86.50 M5.1 6.35 5.98 2.55 0.41 0.20 42.03 115.85 38.62
M05 30.53 1.39 1.17 3.24 0.93 14.75 20.00 33.31 M5.2 6.28 5.99 2.52 0.38 0.18 42.03 110.25 80.78
M06 29.06 1.39 1.33 4.93 1.00 13.68 17.68 57.88 M4 1.97 7.01 2.48 1.63 0.45 38.36 41.50 29.77
M6 20.93 1.23 0.97 8.72 1.30 14.13 12.97 103.26 M3 3.76 4.94 1.58 6.95 1.53 31.31 10.98 122.73
M5 15.38 1.12 0.83 8.42 1.53 11.87 12.37 110.03 M2 1.85 3.49 1.01 6.79 1.72 31.59 9.51 123.04
M4 11.88 1.12 0.77 8.04 1.81 11.82 9.92 114.72 M1 1.95 2.62 0.83 5.54 1.91 27.64 9.90 101.08
M3 6.50 0.83 0.70 8.79 2.03 14.89 16.17 108.16
M2 2.71 0.78 0.68 8.92 2.56 13.51 21.71 106.80
M1 1.70 1.07 0.81 10.14 3.95 9.31 22.94 115.96
Table VI.4 Heavy metals (µg/g) and iron (mg/g) of Bailén samples
A2L1 A2L2
Sample Sample
Zn Cd Pb Cr Fe Zn Cd Pb Cr Fe
M01 48.8 0.9 7.8 9.2 34.15 M01 17.8 21.7 11.1 8.8 35.62
M02 10.3 1.2 5.1 8.2 34.95 M02 3.9 1.0 10.1 12.5 30.46
M03 4.9 1.5 9.6 9.0 32.96 M03 0.8 1.1 9.7 10.7 31.40
M5 0.9 1.0 4.8 10.7 32.36 M04 7.2 5.1 14.2 11.3 32.54
M5 3.4 1.4 20.8 10.2 31.84
M4 4.4 1.1 14.4 9.7 32.52
M3 0.5 1.6 14.1 9.1 31.56
M2 5.2 2.7 13.6 10.6 31.31
M1 2.0 0.7 11.9 11.3 31.55
A2L3 A2L4
Sample Sample
Zn Cd Pb Cr Fe Zn Cd Pb Cr Fe
M01 250.6 163.9 383.4 197.1 39.03 M01 2.7 0.3 9.5 12.3 32.01
M02 127.3 124.6 100.0 55.8 31.94 M02 5580.2 0.9 2.3 10.7 32.29
M03 24.1 14.9 33.9 18.5 30.58 M03 1343.1 3.6 1.7 11.5 33.75
M04 12.6 2.3 27.8 13.6 31.82 M5.1 3.6 4.3 0.5 11.1 32.79
M05 6.1 1.2 27.6 12.9 32.88 M5.2 4.1 1.9 0.8 11.6 31.35
M06 4.5 4.2 26.8 11.2 32.08 M4 8.3 3.2 4.2 12.4 32.03
M6 0.7 6.6 132.4 9.7 30.82 M3 3.1 2.6 10.8 11.6 29.07
M5 4.1 2.1 128.4 10.4 31.69 M2 2.9 0.7 1.2 12.6 30.95
M4 1.9 5.4 132.6 9.1 36.65 M1 3.1 3.9 2.9 12.6 30.12
M3 6.4 2.1 127.2 12.2 32.85
M2 4.4 12.8 34.0 9.4 34.74
M1 5.6 2.7 37.5 10.8 31.40
Table VI.5 Exchangeable cations and cationic-exchange capacities [cmol(+)/kg] of Bailén samples
A2L1 A2L2
Sample Exchangeable cations Sample Exchangeable cations
CIC CIC
M01 <0.01 0.34 0.28 60.06 2.53 <63.22 11.8 M01 <0.01 0 0.72 67.28 5.47 <73.48 13.27
M02 <0.01 0.05 0.25 69.52 4.71 74.53 13.0 M02 <0.01 0.07 0.52 80.22 7.42 88.23 13.47
M03 <0.01 0.01 0.24 69.62 4.6 74.47 14.3 M03 <0.01 0.07 0.49 72.94 8.61 82.11 13.57
M5 0.02 0.11 0.29 71.02 4.02 75.46 13.4 M04 <0.01 0.09 0.48 75.98 5.7 82.25 13.44
M5 0.03 0.08 0.42 69.92 5.35 75.80 12.32
M4 0.04 0.07 0.37 74.35 5.58 80.41 13.68
M3 0.04 0.07 0.37 65 5.87 71.36 12.76
M2 0.06 0.08 0.37 60.84 6.1 67.39 13.07
M1 0.09 0.05 0.34 56.52 5.81 62.42 14.14
A2L3 A2L4
Sample Exchangeable cations Sample Exchangeable cations
CIC CIC
M01 2.16 0.24 0.94 83.17 6.01 92.52 13.5 M01 7.95 1.15 1.69 59.23 5.28 75.30 11.7
M02 1.38 0.33 0.50 76.46 4.56 83.23 13.4 M02 6.62 2.38 1.61 61.68 2.78 75.07 14.5
M03 1.27 0.28 0.50 73.99 4.82 80.86 16.5 M03 5.45 2.62 1.91 43.05 4.21 57.25 15.3
M04 1.05 0.23 0.41 89.67 2.15 93.51 12.6 M5.1 6.18 2.03 2.93 36.07 4.6 51.81 14.2
M05 1.21 0.28 0.62 82.21 4.14 88.46 11.7 M5.2 7.78 1.73 1.79 38.18 4.12 53.60 14.9
M06 1.15 0.23 0.54 69.92 2.64 74.48 11.8 M4 1.30 0.99 1.46 30.84 3.64 38.23 12.8
M6 0.68 0.15 0.36 64.26 1.76 67.21 11.0 M3 1.40 0.67 0.62 31.91 3.9 38.50 12.8
M5 0.49 0.14 0.35 67.28 2.56 70.82 10.1 M2 0.86 0.50 0.44 33.66 5.94 41.40 11.3
M4 0.43 0.18 0.34 57.98 3.31 62.24 10.2 M1 1.05 0.41 0.37 31.73 4.76 38.32 14.1
M3 0.29 0.16 0.32 63.71 3.48 67.96 15.2
M2 0.20 0.15 0.34 68.54 4.11 73.34 11.6
M1 0.16 0.19 0.36 64.62 4.69 70.02 14.7
Table VI.6 Semi-quantitative average mineralogical composition (mass %, DRX) and specific surface (Se: m2/g) of Bailén samples
A2L1 A2L2
Sample Sheet Feldspars Sample Sheet Feldspars
Quartz Calcite Dolomite Pyrite Se Quartz Calcite Dolomite Pyrite Se
M01 47 34 13 4 <1 1 <1 31 M01 46 31 14 5 <1 2 2 33
M02 49 33 13 4 1 <1 1 32 M02 42 34 16 6 <1 1 <1 34
M03 53 28 12 6 <1 0 0 32 M03 47 30 13 7 <1 <1 2 33
M5 55 28 12 3 <1 1 <1 33 M04 52 29 12 5 <1 0 1 32
M5 49 30 14 5 <1 <1 <1 34
M4 44 35 14 5 <1 <1 1 33
M3 45 32 15 6 <1 <1 2 34
M2 49 31 13 5 1 1 1 34
M1 46 32 15 6 <1 1 0 34
A2L3 A2L4
Sample Sheet Feldspars Sample Sheet Feldspars
Quartz Calcite Dolomite Pyrite Se Quartz Calcite Dolomite Pyrite Se
M01crust 44 36 11 4 <1 1 2 n.d. M01 40 38 13 5 1 2 1 17
M01 55 30 10 4 0 1 1 31 M02 47 32 15 3 1 <1 1 22
M02 58 28 10 3 <1 1 <1 35 M03 44 35 14 4 1 <1 2 22
M03 50 31 12 4 <1 1 1 33 M5.1 50 31 13 4 <1 1 1 22
M04 62 19 13 4 <1 <1 1 33 M5.2 45 33 15 3 1 1 1 23
M05 65 16 12 5 <1 <1 1 31 M4 43 33 16 6 <1 1 1 25
M06 64 18 13 3 <1 0 1 30 M3 52 29 13 5 <1 <1 1 26
M6 48 30 14 5 1 <1 2 32 M2 49 32 12 6 <1 <1 1 22
M5 50 30 12 6 <1 1 1 33 M1 48 32 14 4 1 1 1 28
M4 46 31 15 6 <1 <1 1 34
M3 52 26 12 4 <1 5 1 32
M2 61 23 11 3 <1 0 1 32
M1 54 24 12 8 1 1 1 31
Se: specific surface area.

BAILÉN DATA. APPENDIX VI
Intensity (a.u.)
Fig. VI.1 X-ray powder-diffraction patterns (a.u: arbitrary units) of A2L1.

Intensity (a.u.)
APPENDIX VI. BAILÉN DATA
Intensity (a.u.)

Intensity (a.u.)
4000
A2L1M5-Air-dried
A2L1M5-Etileneglycol
3000
2500
2000
1500
1000
500
0
2 4 6 8 10 12 14 16 18 20 22
2 theta
Fig. VI.5 X-ray diffraction patterns of oriented slides of A2L1M5: drying at room temperature, solvation
with etileneglycol and heating to 550ºC for 24 h (Moore and Reynolds, 1997).
3000
A2L2M04-Air-dried
2700 A2L2M04-Etileneglycol
A2L2M04-Heating to 550‫؛‬C
2400
2100
1800
1500
1200
900
600
300
0
2 4 6 8 10 12 14 16 18 20 22
2 theta
with etileneglycol and heating to 550ºC for 24 h (Moore and Reynolds, 1997).
3000
A2L3M01crust-Air-dried
2700 A2L3M01crus-Glycerol
A2L3M01crus-Heating to 550‫؛‬C
2400
2100
1800
1500
1200
900
600
300
0
2 4 6 8 10 12 14 16 18 20 22
2 theta
Fig. VI.7 X-ray diffraction patterns of oriented slides of A2L3M01crust: drying at room temperature,
solvation with glycerol and heating to 550ºC for 24 h (Moore and Reynolds, 1997).
3000
A2L3M01-Air-dried
2700 A2L3M01-Glycerol
2400
2100
1800
1500
1200
900
600
300
0
2 4 6 8 10 12 14 16 18 20 22
2 theta
with glycerol and heating to 550ºC for 24 h (Moore and Reynolds, 1997).
3000
A2L3M02-Air-dried
A2L3M02-Heating to 550ºC
2400
2100
1800
1500
1200
900
600
300
0
2 4 6 8 10 12 14 16 18 20 22
2 theta
with glycerol and heating to 550ºC for 24 h (Moore and Reynolds, 1997).
3000
A2L3M03-Air-dried
2400
2100
1800
1500
1200
900
600
300
0
2 4 6 8 10 12 14 16 18 20 22
2 theta
Fig. VI.10 X-ray diffraction patterns of oriented slides of A2L3M03: drying at room temperature,
3000
A2L4M01-Air-dried
2400
2100
1800
1500
1200
900
600
300
0
2 4 6 8 10 12 14 16 18 20 22
2 theta
3000
A2L4M02-Air-dried
2400
2100
1800
1500
1200
900
600
300
0
2 4 6 8 10 12 14 16 18 20 22
2 theta
3000
A2L4M03-Glycerol
Intensity (arbitrary units) 2400

2100
1800
1500
1200
900
600
300
0
2 4 6 8 10 12 14 16 18 20 22
2 theta
A2L4M5.1-Air-dried
500 A2L4M5.1-Etileneglycol
400
300
200
100
0
2 4 6 8 10 12 14 16 18 20 22
2 theta
Fig. VI.14 X-ray diffraction patterns of oriented slides of A2L4M5.1: drying at room temperature,
solvation with etileneglycol and heating to 550ºC for 24 h (Moore and Reynolds, 1997).
1600
A2L4M5.2-Air-dried
A2L4M5.2-Etileneglycol
1400
1200
1000
800
600
400
200
0
2 4 6 8 10 12 14 16 18 20 22
2 theta
Fig. VI.15 X-ray diffraction patterns of oriented slides of A2L4M5.2: drying at room temperature,
solvation with etileneglycol and heating to 550ºC for 24 h (Moore and Reynolds, 1997).
Intensity (a.u.)
Fig. VI.16 X-ray diffraction patterns (a.u: arbitrary units) of oriented slides of A2L3 and A2L4, compared
with the original clay of Bailén (A2). Clays were studied in three oriented aggregates using standard
methods involving: drying at room temperature, solvation with glycerol (0.1:2 clay-to-water+glycerol
ratio) and heating to 550ºC for 24 h (0.1:2 clay-to-water) (Moore and Reynolds, 1997).
90
80
Transmission (%) 70
60
50
40
30
A2 original
20 A2L3crust
4250
4000
3750
3500
3250
3000
2750
2500
2250
2000
1750
1500
1250
1000
750
500
250
0
-1
Wavenumber (cm )
Fig. VI.17 FTIR spectra of the original Bailén and the A2L3M01crust.
100
90
80
Transmission (%)
70
60
50
40
30
A2 original
20 A2L3M01
4250
4000
3750
3500
3250
3000
2750
2500
2250
2000
1750
1500
1250
1000
750
500
250
0
-1
Wavenumber (cm )
Fig. VI.18 FTIR spectra of the original Bailén and the A2L3M01.
100
90
80
Transmission (%)
70
60
50
40
30
A2 original
20 A2L3M02
4250
4000
3750
3500
3250
3000
2750
2500
2250
2000
1750
1500
1250
1000
750
500
250
0
-1
Wavenumber (cm )
90
80
70
Transmission (%)
60
50
40
30
20
10
A2L3M03
0 A2 original
4250
4000
3750
3500
3250
3000
2750
2500
2250
2000
1750
1500
1250
1000
750
500
250
0
-1
Wavenumber (cm )
90
80
70
Transmission (%)
60
50
40
30
20
10 A2L4M01
0 A2 original
4250
4000
3750
3500
3250
3000
2750
2500
2250
2000
1750
1500
1250
1000
750
500
250
0
-1
Wavenumber (cm )
Fig. VI.21 FTIR spectra of the original bailén and the A2L4M01.
90
80
Transmission (%)
70
60
50
40
30
20 A2L4M02
A2 original
4250
4000
3750
3500
3250
3000
2750
2500
2250
2000
1750
1500
1250
1000
750
500
250
0
-1
Wavenumber (cm )
110
100
90
Transmission (%)
80
70
60
50
40
30 A2L4M03
A2 original
20
4250
4000
3750
3500
3250
3000
2750
2500
2250
2000
1750
1500
1250
1000
750
500
250
0
-1
Wavenumber (cm )
100 110
M02 O1
95 105
90 M01 5
100 O4
4
O3
85 1
WSIC
WSIC
M03 95
80 2
90
3
75
85
70 M5 O2
A2L1 A2L2
65 80
0 5 10 15 20 25 30 35 40 45 50 55 60 0 4 8 12 16 20
Alkalinity 600 Alkalinity
O2
O5 525
160
450
140
O1 375 O3
120 5.1
WSIC
O4 O6 300
WSIC
O2 4
100 O3 1 225
O1
6 2 5.2
4 3 150
80 5
75 13
2
60 A2L4
A2L3 0
0 25 50 75 100 125 150 175
5 10 15 20 25 30 35
Alkalinity
Alkalinity
Fig. VI.24 Graphical representations of WSIC (µg/g) vs. alkalinity (mmol/kg) in the clay samples of the
four columns.
MANOVA, BETWEEN-SUBJECTS AND MULTIPLE TESTS (BAILÉN). APPENDIX VII
APPENDIX VII. MANOVA, BETWEEN-SUBJECTS AND MULTIPLE

TESTS (BAILÉN)
Table VII.1 Multivariate tests
Design: intersection + column

Hypothesis Error Non central Observed
Effect Value F df df Sig. parameter powera
Traza de Pillai 3 4 90 9.0 0.02 333 0.91
Lambda de Wilks 0 15 90 3.9 0.01 1292 0.96
Raíz mayor de Roy 22211 2221b 30 3.0 0.00 66632 1.00
df: degrees of freedom
a
Computed using α = 0.05 (Sig.)
b
The statistic is an upper bound on F that yields a lower bound on the significance level.
Table VII.2 Tests of Between-Subjects Effects

Dependent Type III sum Mean Noncent. Observed
Source
variable of squares df square F Sig. parameter power
pH 1.95 3 0.65 8.07 0.00 24.21 0.98
Eh 23430.21 3 7810.07 20.65 0.00 61.95 1.00
EC 49.74 3 16.58 16.89 0.00 50.67 1.00
WSOC 1029144.83 3 343048.28 71.56 0.00 214.67 1.00
WSIC 131602.84 3 43867.61 5.97 0.00 17.91 0.93
Moisture 440.52 3 146.84 1.03 0.39 3.09 0.25
Sol_NH4+ 7025.12 3 2341.71 3.09 0.04 9.26 0.66
Sol_Na+ 139.86 3 46.62 72.37 0.00 217.10 1.00
Sol_K+ 12.32 3 4.11 30.34 0.00 91.03 1.00
Sol_Ca2+ 123.46 3 41.15 4.85 0.01 14.54 0.86
Sol_Mg2+ 9.78 3 3.26 5.00 0.01 15.00 0.87
Sol_Cl- 5790.91 3 1930.30 72.34 0.00 217.01 1.00
Alcalinity 30343.83 3 10114.61 8.62 0.00 25.87 0.99
Sol_SO42- 4844.58 3 1614.86 1.01 0.40 3.03 0.25
Ex_NH4+ 102.99 3 34.33 12.96 0.00 38.88 1.00
Column
Ex_Na+ 10.31 3 3.44 18.31 0.00 54.94 1.00

Ex_K+ 6.69 3 2.23 11.27 0.00 33.81 1.00
Ex_Ca2+ 5825.96 3 1941.99 22.06 0.00 66.18 1.00
Ex_Mg2+ 35.52 3 11.84 9.65 0.00 28.96 0.99
CEC 3.87 3 1.29 0.58 0.63 1.74 0.16
Sheetsilicates 578.56 3 192.85 8.19 0.00 24.56 0.98
Quartz 333.09 3 111.03 7.45 0.00 22.34 0.97
Sodic-feldspar 0.62 3 0.21 0.33 0.80 1.00 0.11
Potasic-feldspar 0.87 3 0.29 1.32 0.29 3.96 0.31
Calcite 24.69 3 8.23 4.56 0.01 13.68 0.84
Dolomite 8.20 3 2.73 2.17 0.11 6.50 0.50
Pyrite 0.33 3 0.11 2.69 0.06 8.08 0.60
SSA 616.03 3 205.34 55.50 0.00 166.49 1.00
Zn 3728213.00 3 1242737.67 1.35 0.28 4.05 0.32
Cd 5167.18 3 1722.39 1.54 0.22 4.63 0.36
Pb 64806.58 3 21602.19 5.75 0.00 17.26 0.92
Cr 3151.76 3 1050.59 0.98 0.41 2.95 0.24
Fe 17.24 3 5.75 1.59 0.21 4.78 0.38
df: degrees of freedom; WSOC/WSIC: water soluble organic/inorganic carbon; Sol_ion: soluble ion; Ex_ion: exchangeable
ion; SSA: specific surface area
APPENDIX VII. MANOVA, BETWEEN-SUBJECTS AND MULTIPLE TESTS (BAILÉN)
Table VII.3 Multiple comparisons

Bonferroni
Dependent (I) (J) Average Standard Confidence interval 95%

variable Column Column substraction (I-J) error Sig. Lower limit Upper limit
pH A2L1 A2L2 .069 .1704 1.000 -.412 .550
A2L3 .007 .1637 1.000 -.456 .469
*
A2L4 -,511 .1704 .032 -.992 -.030
A2L2 A2L1 -.069 .1704 1.000 -.550 .412
A2L3 -.062 .1250 1.000 -.415 .291
*
A2L4 -,580 .1337 .001 -.958 -.202
A2L3 A2L1 -.007 .1637 1.000 -.469 .456
A2L2 .062 .1250 1.000 -.291 .415
*
A2L4 -,518 .1250 .002 -.871 -.165
*
A2L4 A2L1 ,511 .1704 .032 .030 .992
*
A2L2 ,580 .1337 .001 .202 .958
*
A2L3 ,518 .1250 .002 .165 .871
Eh A2L1 A2L2 7.89 11.686 1.000 -25.12 40.90
A2L3 12.33 11.228 1.000 -19.38 44.05
*
A2L4 67,67 11.686 .000 34.66 100.68
A2L2 A2L1 -7.89 11.686 1.000 -40.90 25.12
A2L3 4.44 8.575 1.000 -19.78 28.67
*
A2L4 59,78 9.167 .000 33.88 85.67
A2L3 A2L1 -12.33 11.228 1.000 -44.05 19.38
A2L2 -4.44 8.575 1.000 -28.67 19.78
*
A2L4 55,33 8.575 .000 31.11 79.56
*
A2L4 A2L1 -67,67 11.686 .000 -100.68 -34.66
*
A2L2 -59,78 9.167 .000 -85.67 -33.88
*
A2L3 -55,33 8.575 .000 -79.56 -31.11
EC A2L1 A2L2 -1.429 .5954 .137 -3.111 .253
*
A2L3 -2,089 .5720 .006 -3.705 -.473
*
A2L4 -3,867 .5954 .000 -5.549 -2.185
A2L2 A2L1 1.429 .5954 .137 -.253 3.111
A2L3 -.660 .4369 .848 -1.894 .574
*
A2L4 -2,438 .4670 .000 -3.757 -1.119
*
A2L3 A2L1 2,089 .5720 .006 .473 3.705
A2L2 .660 .4369 .848 -.574 1.894
*
A2L4 -1,778 .4369 .002 -3.012 -.544
*
A2L4 A2L1 3,867 .5954 .000 2.185 5.549
*
A2L2 2,438 .4670 .000 1.119 3.757
*
A2L3 1,778 .4369 .002 .544 3.012
WSOC A2L1 A2L2 -15.36 41.608 1.000 -132.89 102.17

A2L3 -14.25 39.976 1.000 -127.17 98.67
*
A2L4 -406,58 41.608 .000 -524.11 -289.05
A2L2 A2L1 15.36 41.608 1.000 -102.17 132.89
A2L3 1.11 30.532 1.000 -85.13 87.35
*
A2L4 -391,22 32.640 .000 -483.42 -299.02
A2L3 A2L1 14.25 39.976 1.000 -98.67 127.17
A2L2 -1.11 30.532 1.000 -87.35 85.13
*
A2L4 -392,33 30.532 .000 -478.58 -306.09
*
A2L4 A2L1 406,58 41.608 .000 289.05 524.11
*
A2L2 391,22 32.640 .000 299.02 483.42
*
A2L3 392,33 30.532 .000 306.09 478.58
WSIC A2L1 A2L2 -11.65 51.512 1.000 -157.16 133.86
A2L3 -21.42 49.491 1.000 -161.22 118.38
*
A2L4 -154,69 51.512 .032 -300.20 -9.19
A2L2 A2L1 11.65 51.512 1.000 -133.86 157.16
A2L3 -9.77 37.800 1.000 -116.54 97.01
*
A2L4 -143,04 40.410 .008 -257.19 -28.90
A2L3 A2L1 21.42 49.491 1.000 -118.38 161.22
A2L2 9.77 37.800 1.000 -97.01 116.54
*
A2L4 -133,28 37.800 .008 -240.05 -26.51
*
A2L4 A2L1 154,69 51.512 .032 9.19 300.20
*
A2L2 143,04 40.410 .008 28.90 257.19
*
A2L3 133,28 37.800 .008 26.51 240.05
Moisture A2L1 A2L2 -3.7850 4.65024 1.000 -16.9205 9.3505
A2L3 -2.3958 4.46781 1.000 -15.0160 10.2244
A2L4 -7.4517 4.65024 .717 -20.5872 5.6839
A2L2 A2L1 3.7850 4.65024 1.000 -9.3505 16.9205
A2L3 1.3892 3.41235 1.000 -8.2497 11.0280
A2L4 -3.6667 3.64795 1.000 -13.9710 6.6377
A2L3 A2L1 2.3958 4.46781 1.000 -10.2244 15.0160
A2L2 -1.3892 3.41235 1.000 -11.0280 8.2497
A2L4 -5.0558 3.41235 .893 -14.6947 4.5830
A2L4 A2L1 7.4517 4.65024 .717 -5.6839 20.5872
A2L2 3.6667 3.64795 1.000 -6.6377 13.9710
A2L3 5.0558 3.41235 .893 -4.5830 14.6947
Sol_NH4+ A2L1 A2L2 -.0570 16.55195 1.000 -46.8112 46.6973

A2L3 -21.8445 15.90260 1.000 -66.7645 23.0755
A2L4 -35.2697 16.55195 .248 -82.0239 11.4846
A2L2 A2L1 .0570 16.55195 1.000 -46.6973 46.8112
A2L3 -21.7875 12.14581 .498 -56.0957 12.5207
A2L4 -35.2127 12.98442 .066 -71.8897 1.4643
A2L3 A2L1 21.8445 15.90260 1.000 -23.0755 66.7645
A2L2 21.7875 12.14581 .498 -12.5207 56.0957
A2L4 -13.4252 12.14581 1.000 -47.7334 20.8830
A2L4 A2L1 35.2697 16.55195 .248 -11.4846 82.0239
A2L2 35.2127 12.98442 .066 -1.4643 71.8897
A2L3 13.4252 12.14581 1.000 -20.8830 47.7334
+
Sol_Na A2L1 A2L2 -.2803 .48232 1.000 -1.6427 1.0821
A2L3 -1.1842 .46340 .095 -2.4931 .1248
*
A2L4 -5,1612 .48232 .000 -6.5236 -3.7988
A2L2 A2L1 .2803 .48232 1.000 -1.0821 1.6427
A2L3 -.9039 .35393 .096 -1.9036 .0958
*
A2L4 -4,8809 .37836 .000 -5.9496 -3.8121
A2L3 A2L1 1.1842 .46340 .095 -.1248 2.4931
A2L2 .9039 .35393 .096 -.0958 1.9036
*
A2L4 -3,9770 .35393 .000 -4.9767 -2.9773
*
A2L4 A2L1 5,1612 .48232 .000 3.7988 6.5236
*
A2L2 4,8809 .37836 .000 3.8121 5.9496
*
A2L3 3,9770 .35393 .000 2.9773 4.9767
+
Sol_K A2L1 A2L2 -.4693 .22105 .253 -1.0937 .1551
*
A2L3 -,7898 .21238 .005 -1.3897 -.1899
*
A2L4 -1,7992 .22105 .000 -2.4236 -1.1748
A2L2 A2L1 .4693 .22105 .253 -.1551 1.0937
A2L3 -.3206 .16221 .344 -.7787 .1376
*
A2L4 -1,3299 .17341 .000 -1.8197 -.8401
*
A2L3 A2L1 ,7898 .21238 .005 .1899 1.3897
A2L2 .3206 .16221 .344 -.1376 .7787
*
A2L4 -1,0093 .16221 .000 -1.4675 -.5512
*
A2L4 A2L1 1,7992 .22105 .000 1.1748 2.4236
*
A2L2 1,3299 .17341 .000 .8401 1.8197
*
A2L3 1,0093 .16221 .000 .5512 1.4675
Sol_Ca2+ A2L1 A2L2 -4.5111 1.75101 .091 -9.4571 .4350

A2L3 -4.3794 1.68232 .085 -9.1314 .3726
A2L4 -.7846 1.75101 1.000 -5.7307 4.1615
A2L2 A2L1 4.5111 1.75101 .091 -.4350 9.4571
A2L3 .1317 1.28489 1.000 -3.4978 3.7611
A2L4 3.7265 1.37361 .066 -.1536 7.6065
A2L3 A2L1 4.3794 1.68232 .085 -.3726 9.1314
A2L2 -.1317 1.28489 1.000 -3.7611 3.4978
A2L4 3.5948 1.28489 .053 -.0346 7.2242
A2L4 A2L1 .7846 1.75101 1.000 -4.1615 5.7307
A2L2 -3.7265 1.37361 .066 -7.6065 .1536
A2L3 -3.5948 1.28489 .053 -7.2242 .0346
2+
Sol_Mg A2L1 A2L2 -1.3282 .48514 .062 -2.6985 .0422
A2L3 -1.1771 .46610 .102 -2.4937 .1395
A2L4 -.2203 .48514 1.000 -1.5907 1.1500
A2L2 A2L1 1.3282 .48514 .062 -.0422 2.6985
A2L3 .1511 .35599 1.000 -.8545 1.1567
*
A2L4 1,1078 .38057 .040 .0328 2.1828
A2L3 A2L1 1.1771 .46610 .102 -.1395 2.4937
A2L2 -.1511 .35599 1.000 -1.1567 .8545
A2L4 .9567 .35599 .070 -.0489 1.9623
A2L4 A2L1 .2203 .48514 1.000 -1.1500 1.5907
*
A2L2 -1,1078 .38057 .040 -2.1828 -.0328
A2L3 -.9567 .35599 .070 -1.9623 .0489
-
Sol_Cl A2L1 A2L2 -7.1746 3.10423 .167 -15.9431 1.5939
*
A2L3 -13,6378 2.98245 .000 -22.0623 -5.2133
*
A2L4 -37,1047 3.10423 .000 -45.8732 -28.3362
A2L2 A2L1 7.1746 3.10423 .167 -1.5939 15.9431
*
A2L3 -6,4632 2.27789 .048 -12.8975 -.0288
*
A2L4 -29,9301 2.43516 .000 -36.8087 -23.0515
*
A2L3 A2L1 13,6378 2.98245 .000 5.2133 22.0623
*
A2L2 6,4632 2.27789 .048 .0288 12.8975
*
A2L4 -23,4669 2.27789 .000 -29.9012 -17.0326
*
A2L4 A2L1 37,1047 3.10423 .000 28.3362 45.8732
*
A2L2 29,9301 2.43516 .000 23.0515 36.8087
*
A2L3 23,4669 2.27789 .000 17.0326 29.9012
Alcalinity A2L1 A2L2 6.2514 20.58243 1.000 -51.8877 64.3905

A2L3 .7833 19.77496 1.000 -55.0749 56.6416
*
A2L4 -64,8797 20.58243 .022 -123.0188 -6.7406
A2L2 A2L1 -6.2514 20.58243 1.000 -64.3905 51.8877
A2L3 -5.4681 15.10338 1.000 -48.1305 37.1944
*
A2L4 -71,1311 16.14619 .001 -116.7392 -25.5230
A2L3 A2L1 -.7833 19.77496 1.000 -56.6416 55.0749
A2L2 5.4681 15.10338 1.000 -37.1944 48.1305
*
A2L4 -65,6631 15.10338 .001 -108.3255 -23.0006
*
A2L4 A2L1 64,8797 20.58243 .022 6.7406 123.0188
*
A2L2 71,1311 16.14619 .001 25.5230 116.7392
*
A2L3 65,6631 15.10338 .001 23.0006 108.3255
2-
Sol_SO4 A2L1 A2L2 -35.8413 24.01413 .876 -103.6739 31.9914
A2L3 -33.6061 23.07203 .934 -98.7775 31.5654
A2L4 -18.0059 24.01413 1.000 -85.8386 49.8267
A2L2 A2L1 35.8413 24.01413 .876 -31.9914 103.6739
A2L3 2.2352 17.62156 1.000 -47.5403 52.0107
A2L4 17.8353 18.83824 1.000 -35.3770 71.0476
A2L3 A2L1 33.6061 23.07203 .934 -31.5654 98.7775
A2L2 -2.2352 17.62156 1.000 -52.0107 47.5403
A2L4 15.6001 17.62156 1.000 -34.1754 65.3757
A2L4 A2L1 18.0059 24.01413 1.000 -49.8267 85.8386
A2L2 -17.8353 18.83824 1.000 -71.0476 35.3770
A2L3 -15.6001 17.62156 1.000 -65.3757 34.1754
+
Ex_NH4 A2L1 A2L2 -.0230 .97801 1.000 -2.7856 2.7395
A2L3 -.8667 .93965 1.000 -3.5209 1.7876
*
A2L4 -4,2819 .97801 .001 -7.0444 -1.5193
A2L2 A2L1 .0230 .97801 1.000 -2.7395 2.7856
A2L3 -.8436 .71767 1.000 -2.8708 1.1836
*
A2L4 -4,2588 .76722 .000 -6.4260 -2.0917
A2L3 A2L1 .8667 .93965 1.000 -1.7876 3.5209
A2L2 .8436 .71767 1.000 -1.1836 2.8708
*
A2L4 -3,4152 .71767 .000 -5.4424 -1.3880
*
A2L4 A2L1 4,2819 .97801 .001 1.5193 7.0444
*
A2L2 4,2588 .76722 .000 2.0917 6.4260
*
A2L3 3,4152 .71767 .000 1.3880 5.4424
Ex_Na+ A2L1 A2L2 .0635 .26026 1.000 -.6717 .7987

A2L3 -.0854 .25005 1.000 -.7917 .6209
*
A2L4 -1,2591 .26026 .000 -1.9942 -.5239
A2L2 A2L1 -.0635 .26026 1.000 -.7987 .6717
A2L3 -.1489 .19098 1.000 -.6883 .3906
*
A2L4 -1,3226 .20417 .000 -1.8993 -.7458
A2L3 A2L1 .0854 .25005 1.000 -.6209 .7917
A2L2 .1489 .19098 1.000 -.3906 .6883
*
A2L4 -1,1737 .19098 .000 -1.7131 -.6342
*
A2L4 A2L1 1,2591 .26026 .000 .5239 1.9942
*
A2L2 1,3226 .20417 .000 .7458 1.8993
*
A2L3 1,1737 .19098 .000 .6342 1.7131
+
Ex_K A2L1 A2L2 -.1885 .26732 1.000 -.9436 .5666
A2L3 -.2002 .25683 1.000 -.9256 .5253
*
A2L4 -1,1597 .26732 .001 -1.9148 -.4046
A2L2 A2L1 .1885 .26732 1.000 -.5666 .9436
A2L3 -.0117 .19616 1.000 -.5658 .5424
*
A2L4 -,9712 .20970 .000 -1.5635 -.3788
A2L3 A2L1 .2002 .25683 1.000 -.5253 .9256
A2L2 .0117 .19616 1.000 -.5424 .5658
*
A2L4 -,9595 .19616 .000 -1.5136 -.4054
*
A2L4 A2L1 1,1597 .26732 .001 .4046 1.9148
*
A2L2 ,9712 .20970 .000 .3788 1.5635
*
A2L3 ,9595 .19616 .000 .4054 1.5136
2+
Ex_Ca A2L1 A2L2 -1.6728 5.63826 1.000 -17.5991 14.2536
A2L3 -4.2625 5.41706 1.000 -19.5641 11.0391
*
A2L4 26,8494 5.63826 .000 10.9231 42.7758
A2L2 A2L1 1.6728 5.63826 1.000 -14.2536 17.5991
A2L3 -2.5897 4.13735 1.000 -14.2765 9.0970
*
A2L4 28,5222 4.42301 .000 16.0285 41.0159
A2L3 A2L1 4.2625 5.41706 1.000 -11.0391 19.5641
A2L2 2.5897 4.13735 1.000 -9.0970 14.2765
*
A2L4 31,1119 4.13735 .000 19.4252 42.7987
*
A2L4 A2L1 -26,8494 5.63826 .000 -42.7758 -10.9231
*
A2L2 -28,5222 4.42301 .000 -41.0159 -16.0285
*
A2L3 -31,1119 4.13735 .000 -42.7987 -19.4252
Ex_Mg2+ A2L1 A2L2 -2,2472* .66551 .012 -4.1271 -.3674

A2L3 .2792 .63940 1.000 -1.5269 2.0853
A2L4 -.3934 .66551 1.000 -2.2733 1.4864
*
A2L2 A2L1 2,2472 .66551 .012 .3674 4.1271
*
A2L3 2,5264 .48835 .000 1.1469 3.9058
*
A2L4 1,8538 .52207 .008 .3791 3.3285
A2L3 A2L1 -.2792 .63940 1.000 -2.0853 1.5269
*
A2L2 -2,5264 .48835 .000 -3.9058 -1.1469
A2L4 -.6726 .48835 1.000 -2.0520 .7069
A2L4 A2L1 .3934 .66551 1.000 -1.4864 2.2733
*
A2L2 -1,8538 .52207 .008 -3.3285 -.3791
A2L3 .6726 .48835 1.000 -.7069 2.0520
CEC A2L1 A2L2 -.1728 .89613 1.000 -2.7041 2.3585
A2L3 .4428 .86097 1.000 -1.9892 2.8747
A2L4 -.3728 .89613 1.000 -2.9041 2.1585
A2L2 A2L1 .1728 .89613 1.000 -2.3585 2.7041
A2L3 .6156 .65758 1.000 -1.2419 2.4730
A2L4 -.2000 .70298 1.000 -2.1857 1.7857
A2L3 A2L1 -.4428 .86097 1.000 -2.8747 1.9892
A2L2 -.6156 .65758 1.000 -2.4730 1.2419
A2L4 -.8156 .65758 1.000 -2.6730 1.0419
A2L4 A2L1 .3728 .89613 1.000 -2.1585 2.9041
A2L2 .2000 .70298 1.000 -1.7857 2.1857
A2L3 .8156 .65758 1.000 -1.0419 2.6730
Sheetsilicates A2L1 A2L2 4.108 2.9165 1.000 -4.130 12.347
A2L3 -4.642 2.8021 .648 -12.557 3.273
A2L4 4.497 2.9165 .801 -3.741 12.736
A2L2 A2L1 -4.108 2.9165 1.000 -12.347 4.130
*
A2L3 -8,750 2.1401 .002 -14.795 -2.705
A2L4 .389 2.2879 1.000 -6.074 6.852
A2L3 A2L1 4.642 2.8021 .648 -3.273 12.557
*
A2L2 8,750 2.1401 .002 2.705 14.795
*
A2L4 9,139 2.1401 .001 3.094 15.184
A2L4 A2L1 -4.497 2.9165 .801 -12.736 3.741
A2L2 -.389 2.2879 1.000 -6.852 6.074
*
A2L3 -9,139 2.1401 .001 -15.184 -3.094
Quartz A2L1 A2L2 -.933 2.3203 1.000 -7.487 5.621

A2L3 5.217 2.2293 .157 -1.080 11.514
A2L4 -2.022 2.3203 1.000 -8.576 4.532
A2L2 A2L1 .933 2.3203 1.000 -5.621 7.487
*
A2L3 6,150 1.7026 .007 1.341 10.959
A2L4 -1.089 1.8202 1.000 -6.230 4.053
A2L3 A2L1 -5.217 2.2293 .157 -11.514 1.080
*
A2L2 -6,150 1.7026 .007 -10.959 -1.341
*
A2L4 -7,239 1.7026 .001 -12.048 -2.429
A2L4 A2L1 2.022 2.3203 1.000 -4.532 8.576
A2L2 1.089 1.8202 1.000 -4.053 6.230
*
A2L3 7,239 1.7026 .001 2.429 12.048
Sodic-feldspar A2L1 A2L2 -.067 .4753 1.000 -1.409 1.276
A2L3 -.358 .4566 1.000 -1.648 .931
A2L4 -.178 .4753 1.000 -1.520 1.165
A2L2 A2L1 .067 .4753 1.000 -1.276 1.409
A2L3 -.292 .3487 1.000 -1.277 .693
A2L4 -.111 .3728 1.000 -1.164 .942
A2L3 A2L1 .358 .4566 1.000 -.931 1.648
A2L2 .292 .3487 1.000 -.693 1.277
A2L4 .181 .3487 1.000 -.805 1.166
A2L4 A2L1 .178 .4753 1.000 -1.165 1.520
A2L2 .111 .3728 1.000 -.942 1.164
A2L3 -.181 .3487 1.000 -1.166 .805
Potasic-feldspar A2L1 A2L2 -.475 .2824 .618 -1.273 .323
A2L3 -.492 .2713 .480 -1.258 .275
A2L4 -.519 .2824 .455 -1.317 .278
A2L2 A2L1 .475 .2824 .618 -.323 1.273
A2L3 -.017 .2072 1.000 -.602 .569
A2L4 -.044 .2215 1.000 -.670 .581
A2L3 A2L1 .492 .2713 .480 -.275 1.258
A2L2 .017 .2072 1.000 -.569 .602
A2L4 -.028 .2072 1.000 -.613 .558
A2L4 A2L1 .519 .2824 .455 -.278 1.317
A2L2 .044 .2215 1.000 -.581 .670
A2L3 .028 .2072 1.000 -.558 .613
Calcite A2L1 A2L2 -1.439 .8074 .509 -3.720 .842

A2L3 .342 .7757 1.000 -1.850 2.533
A2L4 -1.439 .8074 .509 -3.720 .842
A2L2 A2L1 1.439 .8074 .509 -.842 3.720
*
A2L3 1,781 .5925 .032 .107 3.454
A2L4 .000 .6334 1.000 -1.789 1.789
A2L3 A2L1 -.342 .7757 1.000 -2.533 1.850
*
A2L2 -1,781 .5925 .032 -3.454 -.107
*
A2L4 -1,781 .5925 .032 -3.454 -.107
A2L4 A2L1 1.439 .8074 .509 -.842 3.720
A2L2 .000 .6334 1.000 -1.789 1.789
*
A2L3 1,781 .5925 .032 .107 3.454
Dolomite A2L1 A2L2 -1.258 .6750 .433 -3.165 .648
A2L3 -.175 .6486 1.000 -2.007 1.657
A2L4 -.192 .6750 1.000 -2.098 1.715
A2L2 A2L1 1.258 .6750 .433 -.648 3.165
A2L3 1.083 .4954 .220 -.316 2.483
A2L4 1.067 .5296 .318 -.429 2.562
A2L3 A2L1 .175 .6486 1.000 -1.657 2.007
A2L2 -1.083 .4954 .220 -2.483 .316
A2L4 -.017 .4954 1.000 -1.416 1.383
A2L4 A2L1 .192 .6750 1.000 -1.715 2.098
A2L2 -1.067 .5296 .318 -2.562 .429
A2L3 .017 .4954 1.000 -1.383 1.416
Pyrite A2L1 A2L2 .064 .1218 1.000 -.280 .408
A2L3 .108 .1170 1.000 -.222 .439
A2L4 -.136 .1218 1.000 -.480 .208
A2L2 A2L1 -.064 .1218 1.000 -.408 .280
A2L3 .044 .0894 1.000 -.208 .297
A2L4 -.200 .0955 .269 -.470 .070
A2L3 A2L1 -.108 .1170 1.000 -.439 .222
A2L2 -.044 .0894 1.000 -.297 .208
A2L4 -.244 .0894 .062 -.497 .008
A2L4 A2L1 .136 .1218 1.000 -.208 .480
A2L2 .200 .0955 .269 -.070 .470
A2L3 .244 .0894 .062 -.008 .497
SSA A2L1 A2L2 -1.1667 1.15590 1.000 -4.4317 2.0984

A2L3 .0000 1.11056 1.000 -3.1370 3.1370
*
A2L4 9,1667 1.15590 .000 5.9016 12.4317
A2L2 A2L1 1.1667 1.15590 1.000 -2.0984 4.4317
A2L3 1.1667 .84820 1.000 -1.2292 3.5626
*
A2L4 10,3333 .90676 .000 7.7720 12.8947
A2L3 A2L1 .0000 1.11056 1.000 -3.1370 3.1370
A2L2 -1.1667 .84820 1.000 -3.5626 1.2292
*
A2L4 9,1667 .84820 .000 6.7708 11.5626
*
A2L4 A2L1 -9,1667 1.15590 .000 -12.4317 -5.9016
*
A2L2 -10,3333 .90676 .000 -12.8947 -7.7720
*
A2L3 -9,1667 .84820 .000 -11.5626 -6.7708
Zn A2L1 A2L2 11.2037 576.79744 1.000 -1618.0735 1640.4810
A2L3 -21.1425 554.16906 1.000 -1586.5014 1544.2165
A2L4 -756.1380 576.79744 1.000 -2385.4152 873.1393
A2L2 A2L1 -11.2037 576.79744 1.000 -1640.4810 1618.0735
A2L3 -32.3462 423.25361 1.000 -1227.9089 1163.2165
A2L4 -767.3417 452.47714 .602 -2045.4520 510.7685
A2L3 A2L1 21.1425 554.16906 1.000 -1544.2165 1586.5014
A2L2 32.3462 423.25361 1.000 -1163.2165 1227.9089
A2L4 -734.9955 423.25361 .556 -1930.5582 460.5672
A2L4 A2L1 756.1380 576.79744 1.000 -873.1393 2385.4152
A2L2 767.3417 452.47714 .602 -510.7685 2045.4520
A2L3 734.9955 423.25361 .556 -460.5672 1930.5582
Cd A2L1 A2L2 -2.8840 20.07023 1.000 -59.5763 53.8082
A2L3 -27.4151 19.28285 .992 -81.8833 27.0531
A2L4 -1.2318 20.07023 1.000 -57.9241 55.4605
A2L2 A2L1 2.8840 20.07023 1.000 -53.8082 59.5763
A2L3 -24.5311 14.72752 .637 -66.1318 17.0697
A2L4 1.6522 15.74438 1.000 -42.8209 46.1253
A2L3 A2L1 27.4151 19.28285 .992 -27.0531 81.8833
A2L2 24.5311 14.72752 .637 -17.0697 66.1318
A2L4 26.1833 14.72752 .513 -15.4175 67.7841
A2L4 A2L1 1.2318 20.07023 1.000 -55.4605 57.9241
A2L2 -1.6522 15.74438 1.000 -46.1253 42.8209
A2L3 -26.1833 14.72752 .513 -67.7841 15.4175
Pb A2L1 A2L2 -6.4917 36.81894 1.000 -110.4940 97.5106

A2L3 -92.4591 35.37449 .083 -192.3813 7.4630
A2L4 3.0733 36.81894 1.000 -100.9290 107.0756
A2L2 A2L1 6.4917 36.81894 1.000 -97.5106 110.4940
*
A2L3 -85,9674 27.01772 .020 -162.2842 -9.6506
A2L4 9.5650 28.88315 1.000 -72.0211 91.1511
A2L3 A2L1 92.4591 35.37449 .083 -7.4630 192.3813
*
A2L2 85,9674 27.01772 .020 9.6506 162.2842
*
A2L4 95,5324 27.01772 .008 19.2156 171.8492
A2L4 A2L1 -3.0733 36.81894 1.000 -107.0756 100.9290
A2L2 -9.5650 28.88315 1.000 -91.1511 72.0211
*
A2L3 -95,5324 27.01772 .008 -171.8492 -19.2156
Cr A2L1 A2L2 -1.1762 19.62730 1.000 -56.6173 54.2650
A2L3 -21.6089 18.85730 1.000 -74.8750 31.6572
A2L4 -2.5527 19.62730 1.000 -57.9938 52.8884
A2L2 A2L1 1.1762 19.62730 1.000 -54.2650 56.6173
A2L3 -20.4327 14.40250 .998 -61.1154 20.2499
A2L4 -1.3765 15.39692 1.000 -44.8681 42.1151
A2L3 A2L1 21.6089 18.85730 1.000 -31.6572 74.8750
A2L2 20.4327 14.40250 .998 -20.2499 61.1154
A2L4 19.0562 14.40250 1.000 -21.6265 59.7389
A2L4 A2L1 2.5527 19.62730 1.000 -52.8884 57.9938
A2L2 1.3765 15.39692 1.000 -42.1151 44.8681
A2L3 -19.0562 14.40250 1.000 -59.7389 21.6265
Fe A2L1 A2L2 1.5161 1.14132 1.000 -1.7078 4.7400
A2L3 .5650 1.09654 1.000 -2.5324 3.6624
A2L4 2.0094 1.14132 .531 -1.2144 5.2333
A2L2 A2L1 -1.5161 1.14132 1.000 -4.7400 1.7078
A2L3 -.9511 .83750 1.000 -3.3168 1.4146
A2L4 .4933 .89532 1.000 -2.0357 3.0224
A2L3 A2L1 -.5650 1.09654 1.000 -3.6624 2.5324
A2L2 .9511 .83750 1.000 -1.4146 3.3168
A2L4 1.4444 .83750 .569 -.9212 3.8101
A2L4 A2L1 -2.0094 1.14132 .531 -5.2333 1.2144
A2L2 -.4933 .89532 1.000 -3.0224 2.0357
A2L3 -1.4444 .83750 .569 -3.8101 .9212
Based on the observed averages.
Error is the mean square = 3.607.
*. The average substraction is significant at α = 0.05.
DENSITY & MAIN PARAMETERS PROFILES (LANDFILLS). APPENDIX VIII
APPENDIX VIII. DENSITY PROFILES RELATED TO OTHER MAIN

PARAMETERS PROFILES IN LANDFILLS
Conversion to SI units:
equivalence
Density: g/cm3 103 kg/m3
Electrical conductivity: mS/cm equivalence 102 mS/m
APPENDIX VIII. DENSITY & MAIN PARAMETERS PROFILES (LANDFILLS)
PCs BIVARIATE PLOTS. APPENDIX IX
APPENDIX IX. BIVARIATE PLOTS OF THE SEVEN PCs
Fig. VIII.1 PC 1 vs. PC 2. Fig. VIII.2 PC 1 vs. PC 3.
Fig. VIII.3 PC 1 vs. PC 4.
Fig. VIII.4 PC 1 vs. PC 5. Fig. VIII.5 PC 1 vs. PC 6. Fig. VIII.6 PC 1 vs. PC 7.
APPENDIX IX. PCs BIVARIATE PLOTS
PCs BIVARIATE PLOTS. APPENDIX IX
APPENDIX IX. PCs BIVARIATE PLOTS
JOURNAL ARTICLE. APPENDIX X
APPENDIX X. JOURNAL ARTICLE: REGADÍO, M. ET AL. (2011)
APPENDIX X. JOURNAL ARTICLE
Waste Management xxx (2011) xxx–xxx
Contents lists available at SciVerse ScienceDirect
Waste Management
journal homepage: www.elsevier.com/locate/wasman
Pollution profiles and physicochemical parameters in old uncontrolled landfills

M. Regadío a,⇑, A.I. Ruiz a, I.S. de Soto a, M. Rodriguez Rastrero a, N. Sánchez b, M.J. Gismera b, M.T. Sevilla b,
P. da Silva b, J. Rodríguez Procopio b, J. Cuevas a
a
Department of Geology and Geochemistry, Faculty of Science, Autónoma University of Madrid, Campus Cantoblanco, C/Fco. Tomás y Valiente 7, 28049 Madrid, Spain
b
Department of Analytical Chemistry and Instrumental Analysis, Faculty of Sciences, Autónoma University of Madrid, Campus Cantoblanco, C/Fco. Tomás y Valiente 7, 28049
Madrid, Spain
a r t i c l e i n f o a b s t r a c t
Article history: The long-term effectiveness of the geological barrier beneath municipal-waste landfills is a critical issue
Received 25 February 2011 for soil and groundwater protection. This study examines natural clayey soils directly in contact with the
Accepted 16 November 2011 waste deposited in three landfills over 12 years old in Spain. Several physicochemical and geological
Available online xxxx
parameters were measured as a function of depth. Electrical conductivity (EC), water-soluble organic car-
bon (WSOC), Cl, NH4+, Na+ and exchangeable NH4+ and Na+ were used as parameters to measure the
Keywords: penetration of landfill leachate pollution. Mineralogy, specific surface area and cationic-exchange capac-
Landfill pollution
ities were analyzed to characterize the materials under the landfills. A principal component analysis,
Clays
Natural liner
combined with a Varimax rotation, was applied to the data to determine patterns of association between
Leachate composition samples and variables not evident upon initial inspection. The main factors explaining the variation in the
data are related to waste composition and local geology. Although leachates have been in contact with
clays for long time periods (13–24 years), WSOC and EC fronts are attenuated at depths of 0.2–1.5 m
within the clay layer. Taking into account this depth of the clayey materials, these natural substrata
(>45% illite–smectite-type sheet silicates) are suitable for confining leachate pollution and for complying
with European legislation. This paper outlines the relevant differences in the clayey materials of the three
landfills in which a diffusive flux attenuation capacity (Ac) is defined as a function (1) of the rate of
decrease of the parameters per meter of material, (2) of the age and area of the landfill and (3) of the
quantity and quality of the wastes.
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction quality of the environment. Landfill sites should comply with these
standards in the short and long terms.
Composite liners comprising a polymeric geomembrane, a clay The multi-barrier concept is one preventive measure. This ap-
liner and a natural geological barrier are crucial components of proach uses consecutive liners that operate independently of one
landfill barrier systems designed to protect surface and groundwa- another and prevent the effects of waste deposits on the surround-
ter. Technical requirements for landfills were established by Euro- ing environment. Under a worst-case scenario, i.e., that all or some
pean legislation throughout the last decade (e.g., 1999/31/EC, of the engineering measures used to contain the deposit fail and
1999; 2003/33/EC, 2002; 2008/1/EC, 2008 and 2008/98/EC, 2008) that the pollutants are released, the geological substratum is the fi-
and tend toward a high level of environmental protection. nal barrier to the migration of pollutants. Therefore, selecting
Directive 1999/31/EC (1999) provides technical standards for the proper locations for landfills is important. These locations should
storage of waste in landfills to protect, preserve and improve the contain substrata that can act as geological, hydrochemical and
natural barriers to ensure the confinement of released waste and
pollutants (Bilitewski et al., 1997).
Directive 1999/31/EC (1999) establishes that, in the case of mu-
Abbreviations: Ac, attenuation capacity; CEC, cationic-exchange capacity; DS,
dissolved solids; EC, electrical conductivity; Ex_cation, exchangeable cation; h, nicipal waste (MW) landfills, this natural liner must have a hydrau-
moisture; K, hydraulic conductivity; LMMOAs, low-molecular-mass organic acids; lic conductivity (K) of 6109 m/s and a depth of P1 m. From a
PC, principal component; PCA, principal component analysis; Rd, ratio decrease per physicochemical point of view, evaluating the long-term effective-
metre deep of parameter X, averaged per landfills; Sol_ion, soluble ion; SSA, specific ness of such a barrier is essential. In addition, the stability of the
surface area; WSIC, water soluble inorganic carbon; WSOC, water soluble organic
carbon.
liner (e.g., potential changes in K) and its retention capacity for
⇑ Corresponding author. Tel.: +34 914976709; fax: +34 914974900. contaminants must be established (Frascari et al., 2004; Munro
E-mail address: mercedes.regadio@uam.es (M. Regadío). et al., 1997; Xie et al., 2009).
0956-053X/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2011.11.008
Please cite this article in press as: Regadío, M., et al. Pollution profiles and physicochemical parameters in old uncontrolled landfills. Waste Management
(2011), doi:10.1016/j.wasman.2011.11.008
2 M. Regadío et al. / Waste Management xxx (2011) xxx–xxx
Contaminants within a landfill take the form of leachates. The and gray-green, micaceous fine sand exhibiting a wavy morphol-
potential pollution caused by leachates is the result of several fac- ogy. The elevation (similar to L3) varies from 595 (N and W) to
tors, including the release of ammonia, chlorinated and non-chlo- 640 m (S and E). Intermittent streams run from the SE to the NW
rinated organic compounds and heavy metal ions into the in the area. The L2 boreholes (L2B1 and L2B2) were drilled at a sim-
environment, all of which are toxic to living organisms (Baccini ilar elevation.
et al., 1987; Christensen et al., 2001; Kjeldsen et al., 1998). L3 is a peri-urban landfill located in an abandoned clay quarry.
The focus of this paper is to evaluate and compare the behavior This landfill sits atop a substrate of Middle Miocene brown and
of natural clay substrata used as natural barriers in three old land- gray clays and micaceous-arkosic sand. The topography is rolling,
fills. Clay minerals are the natural materials with the lowest per- and the elevations vary between 640 and 680 m (similar to L2)
meability as a result of their high specific surface area (SSA). The and generally decline from the SE to the NW. Two boreholes
main objective here is to assess the depth at which natural atten- (L3B1 and L3B2) were drilled, with L3B1 located lower in elevation.
uation of the main components of the pollution front occurs. To- As a result of clay extraction and deposition, the original topogra-
ward this end, we selected locations that lack geomembranes phies of L2 and L3 were extensively modified over large areas be-
and have housed landfill operations for 10–20 years. These charac- fore the landfills were installed.
teristics are important for evaluating the current requirements of Regarding the meteorology, L1 is in an area with a Mediterra-
the EU directive, particularly in light of the fact that there are nean climate, receiving a mean annual rainfall of 650 mm with a
few well-documented, full-scale leachate fronts, and these are minimum of 30 mm in July and a maximum of 90 mm in October.
known primarily from studies of sandy aquifers (Brun et al., L2 and L3 are in an area with a Continental Mediterranean climate,
2002; Christensen et al., 1994; Islam et al., 2001; Marzougui and receiving a mean annual precipitation of 400–430 mm with a min-
Ben Mammou, 2006; van Breukelen et al., 2004). imum of 10–13 mm in August and a maximum of 52–60 mm in
May (L2) and in November (L3). Temperatures are similar among
the three landfills (an annual average of 14 °C, a monthly minimum
2. Materials and sampling of 5–6 °C in January and a monthly maximum of 24 °C in July).
2.1. Materials and site description
The analyzed materials were natural clays that were in direct 2.2. Sampling
contact with landfill leachates. Three landfills that had no compos-
ite polymeric or engineered clay barriers within the landfill vessel The clay barrier samples were obtained from cores extracted
were chosen. The studied landfills were denoted as L1, L2 and L3. with a rotational drill. The drill penetrated the waste and extracted
L1 (NE Spain) has a surface area of 3 ha, received 78,000 t/year of a continuous borehole 0.1 m in diameter and a maximum of 5 m in
mixed industrial and MW and was 23 years old at the time when length. Basic information about the boreholes is shown in Table 1.
the samples were taken. L2 (central Spain) occupies 20 ha, received The cores were not contaminated by the mud used in the lubri-
solely MW (135,000 t/year) and was 24 years old. L3 (central cation of the drilling head (Fig. 1a). To prevent cross-pollution, la-
Spain) occupies 36 ha, received 145,000 t/year of mainly MW and tex gloves were used while handling the cores, marking the depths
was 13 years old. or distributing the samples. The cores were immediately wrapped
In all cases, leachates saturated the waste at least 1 m above the within an LDPE plastic film to preserve the moisture and were
clay surfaces. These leachates were named for their corresponding transported to the laboratory in HDPE calibrated boxes measuring
landfill followed by an L (L1L, L2L and L3L) and were sampled and 1 m 0.5 m, which were divided into five longitudinal sections of
analyzed (Section 4.1). Table 1
L1 is a peri-urban landfill that was developed in a defunct clay Period of time of the borehole extractions, waste heights, borehole lengths and the
quarry. The dominant lithology consists of Tertiary (Oligocene) number of samples collected.
clayey and silty materials. The landfill is within the natural topog- Landfill Borehole Month Waste Borehole No. of
raphy (or a shallow excavation), which is characterized by low re- thickness (m) depth (m) samples
lief; the highest elevation in the NW (130 m) and the lowest in the
L1 B1 November 17 3 10
SE (110 m) determine the drainage network. L1 is much lower in B2 14 5 11
elevation than L2 and L3 (595–640 m and 640–680 m, respec- B3 11 3.2 9
tively). Three boreholes were drilled in L1: L1B1, L1B2 and L1B3, L2 B1 April 42 5 14
B2 45 3.5 12
in that order from the bottom to the top of a smoothly sloping area.
L3 B1 May 28 5 13
L2 is also located in an abandoned clay quarry. The lithology B2 27 4.9 14
corresponds to Tertiary (Middle Miocene) brown clays with silt
Fig. 1. (a) Appearance of a just-extracted core. (b) A core wrapped within a LDPE film and inside the transport box.
(2011), doi:10.1016/j.wasman.2011.11.008
M. Regadío et al. / Waste Management xxx (2011) xxx–xxx 3
the same thickness as the cores (Fig. 1b). One core was transported measured. Sol_Na+ and Sol_K+ were analyzed using a Buck Scien-
per box, and the boxes were carefully closed and sealed. tificÒ PFP-7 flame photometer with 0.5, 1 and 2 mM Na/KCl stock
Within the same day, the cylindrical cores were divided into solutions. Sol_Ca2+ and Sol_Mg2+ were determined using Flame
samples of different thicknesses and from different depths (Appen- Atomic Absorption Spectroscopy (Unicam™ Solaar M series atom-
dix A: Tables A.1.1, A.2.1 and A.3.1). Beginning at the point of waste ic-absorption spectrometer) with 5, 15, 20, 30 and 40 mg/L Ca2+
contact, the cores were sliced into four 0.025-m sections (samples stock solutions and 0.5, 0.75, 1, 1.5 and 2 mg/L Mg2+ stock solutions,
M01, M02, M03 and M04) and subsequently into three or more respectively. Sol_NH4+ was estimated using an ion-selective poten-
consecutive sections measuring 0.05 m in thickness (M05, tiometer (ORIONÒ 9512 Ammonia Gas Sensing Electrode) with 101,
M06. . .). Another cylindrical section was taken at a depth of 102, 103, 104 and 105 mol/L stock solutions. Alkalinity was
0.75–1 m. Beginning at this depth, 0.10-m-thick sections were determined by titration with an ORIONÒ 960 potentiometer using
sampled by slicing every 1 m. Although the cores were not coated a normalized H2SO4 solution (between 103 and 102 M) as the ti-
in drilling mud, the external surfaces of the samples were removed. trant and a pH meter to obtain the titration curve. The endpoint of
The samples were preserved in the dark and were refrigerated the titration is the minimum point on a plot of the derivative of
(4 °C) until analyses were conducted. the pH vs. the volume of the consumed titrant (corresponding to a
The sampling of leachates was performed using piezometers or pH value 4.8).
wells located near the boreholes. One liter was collected in opaque To avoid any alteration of the original conditions, and particu-
bottles with a pump and silicone tubing. The bottles were over- larly to avoid the modification of alkalinity or aqueous NH4+ by a
flowed and closed with a Teflon hermetic top, making sure that previous heating treatment, these liquid extracts were obtained
no air was left inside. The instruments for each sampling were used from wet samples.
only once.
3.2. Characterization of the solids
3. Methods
The solids remaining after the extraction of the soluble cations
3.1. Analyses of aqueous extracts and alkalinity were used to determine the exchangeable cations
(Ex_NH4+, Ex_Na+, Ex_K+, Ex_Ca2+, Ex_Mg2+) and the cationic-ex-
Physicochemical measurements of pH, redox potential and change capacity (CEC). The exchangeable cations were extracted at
electrical conductivity were determined in duplicate at laboratory room temperature from 10 g of the original wet clay to a 100-mL
temperature in aqueous solutions from 10 g of solid sample (with solution, as described by Thomas (1982). Ex_Na+, Ex_K+, Ex_Ca2+
a soil-to-deionized water ratio of 1:2.5) following methods pub- and Ex_Mg2+ were replaced by NH4+ homoionization after three cy-
lished by the Ministerio de Agricultura, Pesca y Alimentación cles of shaking and centrifugation of the soil in contact with 25 mL of
(1994). The solid samples used in these analyses and in the determi- NH4Ac, 1 M and pH = 7. After each cycle, the supernatant was poured
nations of soluble carbon species and major soluble anions were first into a 100-mL volumetric flask, which was then filled with deionized
air dried for 7 days. pH was measured using a glass combined elec- water (25 mL). The suspension was filtered through a 0.45-lm fil-
trode calibrated with standard solutions of pH 4, 7 and 10. The redox ter. The Ex_NH4+ was extracted in the other 10-g replicate from the
potential was analyzed using a combined platinum electrode and soluble species. In this case, the soil was homoionized with Na+,
calibrated using a 220-mV (pH 7, 25 °C) CRISON standard. Both repeating three cycles of stirring and centrifugation with a dilution
parameters were measured in the supernatant that resulted from of 25 mL of 1 M NaAc at pH = 8.2. After each cycle, the supernatant
shaking the 1:2.5 solution for 10 min and allowing it to settle for was transferred into a 100-mL volumetric flask, and deionized water
30 min. The solution was centrifuged and filtered through a polypro- was added until the graduation mark (25 mL). Again, the solution
pylene membrane with a pore size of 0.45 lm before measuring the was filtered. The exchangeable cations were analyzed using the
EC with a multi-range cell (calibrated with potassium chloride same procedures described for the soluble-ion determinations.
standards). The CEC was determined in the remaining solid after the
The major soluble anions (primarily Sol_Cl and Sol_SO2 4 ) were Ex_NH4+ extraction. The additional Na+ not present in the
determined by ion chromatography (METROHM™ 761 Compact IC) exchangeable sites was removed by successive washings in 100%
in an aqueous extract composed of a 1:10 soil-to-deionized-water ethanol until the measured EC was <30 lS/cm. The Na+ was then
ratio. The extracts were prepared from 2.5 g of sample and 25 mL displaced by Mg2+ with a Mg(NO3)25H2O solution (0.5 M, pH = 5)
of deionized water in sealed polypropylene centrifuge bottles, at room temperature (Rhoades, 1982). The final Na+ concentration
which were shaken for 24 h. The extracts were then centrifuged was equivalent to the CEC and was measured in the previously
at 3500 rpm for 15 min, and 20 mL of the supernatant was filtered mentioned flame photometer.
through a 0.45-lm membrane for analysis. Water-soluble carbon To reference these data and the liquid solution data (Section 3.1)
species were quantified in a ShimadzuÒ TOC-5000 carbon analyzer with respect to the dry solid-sample mass, the gravimetric water
from aqueous solutions obtained using the same treatment as content was also measured in duplicate. A 5-g portion of the origi-
above but with a 1:5 solid-to-deionized-water ratio. The apparatus nal sample was weighed to an accuracy of ±0.01 g (mm). The same
was calibrated with stock solutions of potassium hydrogen phthal- fraction was weighed again after being dried at 105 °C for 48 h
ate for water-soluble total carbon (WSTC) determination and with (md). Moisture (h) was estimated using the following formula:
stock solutions of sodium hydrogen carbonate and sodium carbon- h = (mm md)/md100 (Ministerio de Agricultura, Pesca y
ate for water-soluble inorganic carbon (WSIC) determination. The Alimentación (1994))
water-soluble organic carbon (WSOC) content in the sample was The samples dried at 105 °C were mechanically ground at a fre-
determined by the difference between the WSTC and the WSIC. quency of 20/s for 5 min using a Retsch MM200 grinder to obtain a
Soluble cations and alkalinity were analyzed from an aqueous homogeneous particle size for specific-surface and global-mineral-
solution with a soil-to-deionized-water ratio of 1:10. The soil was ogy analyses. For the clay-mineralogy analysis, sections were taken
obtained from the original refrigerated samples (without drying). from the original wet samples.
The aqueous solutions were prepared by moisturizing 10 g of soil The SSA was measured in duplicate. Approximately 0.20 g of the
with 100 mL of water and allowing it to settle in a refrigerator for ground material was then dried at 90 °C for 24 h and degassed
24 h. Next, the solution was shaken for 24 h, centrifuged and passed under an N2 flow for 18 h at 90 °C (UNE 22-164-94) using a
through a 0.45-lm filter. Two replicates from each sample were Micromeritics™ Flow-Prep 060 station. Finally, the material was
(2011), doi:10.1016/j.wasman.2011.11.008
weighed to within 0.0001 g. The SSA was measured by the Bru- Table 2
nauer-Emmett-Teller (BET) method of nitrogen gas adsorption. Chemical analyses of the landfill leachates.
The measurement was carried out at 77 K using a MicromeriticsÒ Parameters L1L L2L L3L
GEMINI V and standard analysis protocol software that obtains a O2 (mg/L) n.d. 0.07 0.50
five-point N2 adsorption isotherm. pH 7.20 7.90 6.70
The X-ray powder diffraction (XRD) technique was applied for EC (mS/cm) 12.97 31.00 4.12
the mineralogy analyses, and the software DRXWINÒ (Primo, WSOC (mg/L) 1260 1744 3360
Alkalinity 44,012 43,920 27,450
2001) was used to analyze the data. XRD was performed using a Cl (mg/L) 9850 5700 269
Philips X’Pert diffractometer with a Ni-filtered CuKa radiation SO2 225 1790 <5
4 (mg/L)
(k = 0.15406 nm). The diffractometer operated at 40 kV and NH4+ (mg/L) 117 1786 160
40 mA with a step size of 0.016 ° and a speed of 2 s/step. Although 2+
Ca (mg/L) 305 86 87
a 10% relative error was assumed for these semi-quantification Mg2+ (mg/L) 280 465 19
K+ (mg/L) 450 1250 95
methods, the comparative differences between samples could be
Na+ (mg/L) 7700 3800 195
observed when the pattern profiles were plotted together. Phenols 1456 1.30 13
The random-powder method was applied to estimate the over- Benzene <0.5 0.01 0.83
all mineralogical composition of the pre-dried and ground samples. Toluene <0.5 0.19 0.81
The semi-quantifications of the minerals were performed accord- Etilbenzene <0.5 0.06 0.10
Xylene <0.5 0.17 2.10
ing to Schultz (1964). A small quantity of ZnO (0.1 g) was mixed Cr 0.04 0.83 0.03
as an internal standard with 1 g of the bulk-ground sample to com- Pb 0.43 <0.10 <0.10
pare and to verify the differences between the very similar random Zn 0.32 <0.02 0.10
powder diffraction patterns observed (Srodon et al., 2001). The pat- Cd <0.02 <0.02 <0.02
terns were normalized with respect to the area of the ZnO reflec- n.d.: Not detected.
tion at 0.2475 nm in the original powder pattern. The X-ray
intensities were recorded over a range of 3 to 70 2h (°). redox potentials. The leachates are alkaline, except for sample
The oriented-slide method was used to determine the specific L3L, which is slightly acidic. The EC varies between the different
families of clay minerals from selected original samples. The estima- leachates: L2L has the greatest value, followed by L1L and, finally,
tion of the clay mineral content in the <2-lm fraction was performed L3L. The lower inorganic ion concentration of L3L relative to the
as proposed by UNE 22-161-92 with the scattering correction factors concentrations of the other landfills explains the EC of L3L. Organic
of Barahona (1974). Clay mineralogy is reported in terms of mass matter was measured as WSOC, which is found in high concentra-
percentage relative to the total mineral content in the sample. Three tions (>1200 mg/L), especially in L3L (Table 2).
glass slides per sample were prepared with the <2-lm size fraction The major inorganic ions Cl, Na+, K+, Ca2+, Mg2+, SO2 4 and NH4
þ
(saturated in Mg2+ solution). Each slide underwent a different pro- are present in significant concentrations (Table 2). In all cases, the
cess: (a) air drying (0.1:2 clay-to-deionized-water ratio), (b) drying dominant component is the alkalinity, whose concentration is one
for 2 h at 550 °C (0.1:2) and (c) glycerol solvation (0.1:2 clay-to- order of magnitude higher than the next most concentrated spe-
water + glycerol ratio), following Moore and Reynolds (1997). The cies, Cl and Na+. The alkalinity is mainly composed of organic acid
XRD intensities were recorded over a range between 3 and 20 2h (°). anions, as HCO 3 was estimated to contribute only 14, 6 and 2% of
the total alkalinity of L1L, L2L and L3L, respectively. From this point
on, L1L is observed to possess a compositional trend different from
3.3. Data treatment
that of the other two leachates: L1L has more K+, Ca2+ and Mg2+
than SO24 and NHþ 4 , whereas L2L and L3L have more significant
A multivariate statistical procedure using Statistical Package for
quantities of NHþ + 2+
4 than K , Ca , Mg
2+
and SO2
4 . L2L is the only
Social Sciences, SPSS 16.0Ó for WINDOWS (SPSS Inc., Chicago, IL
studied landfill with a high concentration of SO24 , i.e., much higher
60606-6412, 2007) was performed. To study the differences be-
than the concentrations measured in L1L and L3L.
tween the landfills, a principal component analysis (PCA) was per-
Xenobiotic organic compounds (except for phenol in L1L) and
formed, followed by a Varimax rotation. The analysis consisted of
heavy metals (<1 mg/L) were found in low concentrations (Table 2).
transforming the possibly correlated variables into a smaller num-
Thus, these compounds were not measured in the soil samples.
ber of uncorrelated variables (called principal components or PCs)
that could describe the behavior of all of the original variables. The
4.2. Mineralogy of the landfill substrata
Varimax rotation was applied to determine which main variables
correspond with the PCs. This analysis reveals the internal struc-
The X-ray powder-diffraction patterns of the three studied
ture of the data in such a way that the variance within the data
landfills (Appendix A: Fig. A.1.1, Fig. A.1.3, Fig. A.2.1, Fig. A.2.3,
is well explained and little information is lost. This technique facil-
Fig. A.3.1, Fig. A.3.3) show an average clay content of >45%, with
itates the interpretation of all of the data and variables as well as
quartz and calcite as the main accessory minerals. Table 3 displays
the variation of the variables within the data. The variables consid-
the average mineralogy of the materials that were in contact with
ered included pH, Eh, EC, WSOC, WSIC, h, Sol_NH4+, Sol_Na+, Sol_K+,
the waste for each landfill. The X-ray oriented-diffraction patterns
Sol_Ca+2, Sol_Mg2+, Sol_Cl, alkalinity, Sol_SO2 +
4 , Ex_NH4 , Ex_Na ,
+
+ 2+ 2+ (Appendix A: Fig. A.1.2, Fig. A.1.4, Fig. A.2.2, Fig. A.2.4, Fig. A.3.2,
Ex_K , Ex_Ca , Ex_Mg , CEC, sheet silicates, quartz, Na-feldspar,
Fig. A.3.4) show that in the <2-lm size, illite (1.0 nm, non-expand-
K-feldspar, calcite and dolomite content, SSA and depth.
able with glycerol solvation) is the predominant clay mineral,
followed by smectite (an expandable mineral that changes its basal
4. Results d-spacing from 1.4 to 1.8 nm under glycerol solvation) and a
smaller fraction of kaolinite and/or chlorite (0.71 nm).
4.1. Leachates
4.3. Leachate infiltration: pollution profiles and attenuation depths
Table 2 presents the analytical results obtained for the leach-
ates. Dissolved oxygen is present in low concentrations in all of The contaminants are considered to be ‘‘attenuated’’ here when
the leachates, which indicates anaerobic conditions and reducing the analyzed parameters (1) have a virtually null variation with
(2011), doi:10.1016/j.wasman.2011.11.008
Table 3
The average mineralogical composition (mass %) of the landfill substrata.
Substrata Sheet silicates No sheet silicates

P
L1 Illite Smectite Chlorite Quartz Nafeldspar Kfeldspar Calcite Dolomite Others
25 ± 3 14 ± 5 8±2 47 ± 17 28 ± 14 3±1 2±2 19 ± 7 1±1
P
L2 Illite Smectite Kln + Chl Quartz Nafeldspar Kfeldspar Calcite Dolomite Others
35 ± 3 7±5 6±2 48 ± 18 43 ± 16 4±2 3±2 0±0 1±1 Sd <1, Hem <1
P
L3 Illite Smectite Chlorite Quartz Nafeldspar Kfeldspar Calcite Dolomite Others
52 ± 2 15 ± 5 8±3 75 ± 25 17 ± 19 3±5 2±3 2±3 1±1
P
: sum of sheet silicates, Kln + Chl: Kaolinite & chlorite, Sd: siderite, Hem: hematite.
To evaluate the capacity of the natural liner to attenuate the

depth and (2) reach low levels with regard to the values measured migration of contaminants, the variations in the analyzed param-
at the waste contact. For clarity, ‘‘the initial value’’ of a parameter is eters vs. depth were depicted, assuming that the main hydraulic
this highest value measured at the waste contact, the ‘‘background gradients are vertical (Marzougui and Ben Mammou, 2006;
value’’ of a parameter is the value that the parameter reaches when Munro et al., 1997; Straub and Lynch, 1982) or considering
it is attenuated, and the ‘‘attenuation depth’’ is the distance in me- diffusion as the main transport process. K was measured using
ters from the waste contact to the depth at which attenuation a test sample taken at an average depth of 0.6 m. The average
occurs. K values were 0.6 109 m/s (L1), 2.5 109 m/s (L2) and
The average values of the measured parameters, classified by 1.0 109 m/s (L3), which were low enough to assume the pre-
depths, from the three landfills are shown in Table 4. dominance of diffusion transport processes (GEOCISA and UAM,
Table 4
The means and standard deviations of measured parameters in the landfill substrata, classified by depth.
Variables Depth (m) L1a L2 L3

pH 0–0.5 8.6 ± 0.1 9.0 ± 0.1 8.5 ± 0.1
0.5–1.25 8.8 ± 0.2 8.8 ± 0.2 8.7 ± 0.1
1.25–2 9.2 ± 0.1 9.0 ± 0.0 8.7 ± 0.4
2–5 9.5 ± 0.3 8.9 ± 0.1 8.7 ± 0.2
Eh (mv) 0–0.5 107 ± 33 141 ± 20 153 ± 22
0.5–1.25 153 ± 27 166 ± 14 177 ± 21
1.25–2 201 ± 85 165 ± 0.0 164 ± 8
2–5 166 ± 26 159 ± 12 161 ± 12
EC (mS/cm) 0–0.5 7.3 ± 2.4 1.5 ± 0.5 1.2 ± 0.4
0.5–1.25 9.3 ± 4.8 1.2 ± 0.1 0.5 ± 0.2
1.25–2 0.7 ± 0.1 1.0 ± 0.0 0.4 ± 0.2
2–5 0.5 ± 0.3 1.1 ± 0.2 0.3 ± 0.1
WSOC (lg/g) 0–0.5 303 ± 139 304 ± 186 305 ± 250
0.5–1.25 189 ± 147 58 ± 19 102 ± 59
1.25–2 112 ± 19 98 ± 0.0 73 ± 26
2–5 116 ± 24 112 ± 81 71 ± 25
WSIC (lg/g) 0–0.5 390 ± 436 272 ± 82 307 ± 177
0.5–1.25 955 ± 892 87 ± 37 183 ± 86
1.25–2 135 ± 8 84 ± 0 170 ± 87
2–5 130 ± 56 98 ± 55 131 ± 70
h (%) 0–0.5 18.9 ± 5.2 21.6 ± 1.5 33.5 ± 7.5
0.5–1.25 27.0 ± 6.1 17.1 ± 8.6 36.7 ± 8.6
1.25–2 18.6 ± 3.5 21.6 ± 0.0 29.7 ± 14.2
2–5 15.4 ± 3.6 23.2 ± 3.7 31.2 ± 7.1
Sol_NH4+ (mmol/kg) 0–0.5 8.1 ± 2.3 40 ± 24 39 ± 32
0.5–1.25 5.6 ± 5.0 3.8 ± 3.4 5.3 ± 7.6
1.25–2 0.2 ± 0.3 2.6 ± 0.0 2.1 ± 2.9
2–5 0.1 ± 0.2 4.4 ± 4.2 1.1 ± 0.9
Sol_Na+ (mmol/kg) 0–0.5 246 ± 93 30 ± 10 19 ± 5
0.5–1.25 311 ± 198 14 ± 7 10 ± 2
1.25–2 22 ± 3 9±0 7±2
2–5 17 ± 10 16 ± 6 6±3
Sol_K+ (mmol/kg) 0–0.5 5.7 ± 1.5 8.8 ± 4.2 8.3 ± 5.5
0.5–1.25 4.1 ± 2.5 2.5 ± 0.4 1.6 ± 0.8
1.25–2 0.7 ± 0.0 2.1 ± 0.0 1.5 ± 0.3
2–5 0.9 ± 0.3 2.4 ± 1.3 1.6 ± 0.7
Sol_Ca2+ (mmol/kg) 0–0.5 7.5 ± 1.4 9.2 ± 15.3 5.1 ± 2.5
0.5–1.25 8.5 ± 6.9 11.2 ± 9.3 5.4 ± 1.9
1.25–2 3.5 ± 2.0 18.1 ± 0.0 5.1 ± 1.8
2–5 3.6 ± 1.3 14.8 ± 15.6 5.1 ± 2.7
Sol_Mg2+ (mmol/kg) 0–0.5 8.8 ± 10.0 3.1 ± 2.5 7.1 ± 3.8
0.5–1.25 8.5 ± 10.4 4.7 ± 1.3 8.5 ± 2.2
1.25–2 2.8 ± 0.3 6.4 ± 0.0 8.2 ± 4.5
2–5 2.3 ± 0.4 5.7 ± 1.3 8.9 ± 4.4
Sol_Cl (mmol/kg) 0–0.5 388 ± 128 14.1 ± 4.8 10.7 ± 7.3
0.5–1.25 419 ± 258 7.9 ± 4.4 6.9 ± 2.2
(continued on next page)
(2011), doi:10.1016/j.wasman.2011.11.008
Table 4 (continued)
Variables Depth (m) L1a L2 L3

1.25–2 26.5 ± 25 4.9 ± 0 4.4 ± 1.9
2–5 8.2 ± 7.6 5.1 ± 2.1 2.6 ± 1.1
Alk (mmol/kg) 0–0.5 26 ± 7 53.8 ± 21.4 53.4 ± 27.4
0.5–1.25 23 ± 8 12.5 ± 3.5 26.9 ± 15.4
1.25–2 15 ± 2 12.2 ± 0 23.7 ± 12.6
2–5 10 ± 1 12.2 ± 6.6 23.6 ± 13.3
Sol_SO2 0–0.5 2.2 ± 4.3 4.9 ± 2.0 0.7 ± 0.8
4 (mmol/kg)
0.5–1.25 10.2 ± 5.7 9.9 ± 1.4 0.2 ± 0.1
1.25–2 1.0 ± 1.4 9.1 ± 0.0 0.1 ± 0.1
2–5 0.2 ± 0.4 11.1 ± 1.7 0.2 ± 0.2
Sol_F (mmol/kg) 0–0.5 2.0 ± 1.5 n.d. n.d.
0.5–1.25 2.6 ± 2.3 n.d. n.d.
1.25–2 0.4 ± 0.2 n.d. n.d.
2–5 0.2 ± 0.1 n.d. n.d.
Ex_NHþ
4 (cmol(+)/kg)
0–0.5 0.48 ± 0.10 2.8 ± 1.6 3.7 ± 2.5
0.5–1.25 0.46 ± 0.27 0.4 ± 0.3 1.1 ± 1.5
1.25–2 0.05 ± 0.07 0.1 ± 0.0 0.5 ± 0.7
2–5 0.00 ± 0.08 0.3 ± 0.2 0.3 ± 0.2
Ex_Na+(cmol(+)/kg) 0–0.5 3.6 ± 2.1 1.01 ± 0.37 0.69 ± 0.26
0.5–1.25 5.5 ± 2.4 0.40 ± 0.24 0.23 ± 0.22
1.25–2 1.1 ± 0.5 0.05 ± 0.00 0.41 ± 0.47
2–5 0.7 ± 1.1 0.34 ± 0.31 0.19 ± 0.17
Ex_K+(cmol(+)/kg) 0–0.5 0.62 ± 0.30 0.99 ± 0.44 1.41 ± 0.64
0.5–1.25 0.79 ± 0.38 0.37 ± 0.08 0.69 ± 0.13
1.25–2 0.31 ± 0.02 0.25 ± 0.00 0.54 ± 0.37
2–5 0.33 ± 0.11 0.35 ± 0.23 0.47 ± 0.22
Ex_Ca2+(cmol(+)/kg) 0–0.5 32.8 ± 7.8 17.1 ± 9.3 21.2 ± 9.6
0.5–1.25 39.9 ± 10.6 11.5 ± 4.4 23.7 ± 2.5
1.25–2 50.6 ± 8.6 6.1 ± 0.0 17.7 ± 12.5
2–5 42.9 ± 2.9 13.9 ± 6.5 13.9 ± 11.0
Ex_Mg2+(cmol(+)/kg) 0–0.5 5.8 ± 2.0 10.5 ± 3.4 22.1 ± 8.4
0.5–1.25 13.4 ± 5.3 11.2 ± 3.6 27.3 ± 5.3
1.25–2 19.7 ± 0.7 6.6 ± 0 23.5 ± 17.8
2–5 11.9 ± 7.1 9.1 ± 6.3 16.9 ± 11.0
CEC (cmol (+)/kg) 0–0.5 10.6 ± 3.8 10.6 ± 2.5 30.2 ± 15.6
0.5–1.25 20.8 ± 3.9 9.0 ± 4.0 34.4 ± 13.7
1.25–2 22.8 ± 0.3 3.2 ± 0.0 13.6 ± 8.9
2–5 13.4 ± 10.1 6.8 ± 4.9 11.2 ± 6.9
Sheet silicates (m %) 0–0.5 32 ± 9.40 55 ± 13.40 77 ± 23.29
0.5–1.25 58 ± 14.15 47 ± 15.36 95 ± 1.63
1.25–2 62 ± 2.47 23 ± 0 66 ± 42.14
2–5 45 ± 26.65 35 ± 23.08 65 ± 29.29
Quartz (m %) 0–0.5 41 ± 12.70 37 ± 12.10 14 ± 17.18
0.5–1.25 17 ± 3.98 43 ± 14.85 4 ± 2.05
1.25–2 19 ± 0.85 67 ± 0 25 ± 33.73
2–5 32 ± 21.29 54 ± 20.71 24 ± 23.38
Na-Feldspar (m %) 0–0.5 4 ± 1.90 3 ± 1.53 3 ± 5.18
0.5–1.25 2 ± 0.73 5 ± 2.72 1 ± 0.50
1.25–2 2 ± 0.57 5±0 2 ± 2.69
2–5 3 ± 0.55 5 ± 2.02 4 ± 5.24
K-Feldspar (m %) 0–0.5 4 ± 2.80 3 ± 1.79 2 ± 1.70
0.5–1.25 1 ± 0.22 3 ± 2.14 1 ± 0.14
1.25–2 1 ± 0.21 5±0 5 ± 6.58
2–5 1 ± 0.67 4 ± 3.89 4 ± 3.31
Calcite (m %) 0–0.5 19 ± 6.10 <1 ± 0.55 2 ± 2.64
0.5–1.25 21 ± 11.55 <1 ± 0.00 <1 ± 0.57
1.25–2 14 ± 0.14 <1 ± 0 <1 ± 0.57
2–5 18 ± 6.86 <1 ± 0.00 2 ± 3.62
Dolomite (m %) 0–0.5 0.1 ± 0.20 1 ± 1.01 1 ± 0.73
0.5–1.25 1 ± 1.39 2 ± 1.66 <1 ± 0.50
1.25–2 3 ± 3.54 <1 ± 0 1 ± 0.28
2–5 1 ± 2.02 1 ± 1.01 1 ± 0.85
SSA (m2/g) 0–0.5 11 ± 4.30 42 ± 13.15 69 ± 26.25
0.5–1.25 24 ± 7.23 40 ± 23.23 92 ± 16.62
1.25–2 31 ± 0.23 11 ± 0 64 ± 53.03
2–5 20 ± 16.67 25 ± 28.94 48 ± 36.83
Eh: redox potential, EC: electrical conductivity, WSOC/WSIC: water soluble organic/inorganic carbon, h: moisture, CEC: cationic-exchange capacity, Alk: alkalinity, SSA:
specific surface area, n.d.: not detected.
a
L1B3 was not included as it was not affected by the leachate.
+
2010). Fig. 2 shows the material-characterization parameters parameters as soluble ions (Sol_Cl, Sol_NHþ
4 and Sol_Na ) on
(the percentages of sheet silicates and SSA on the top X-axis the top X-axis and exchangeable cations (Ex_NH4 and Ex_Na+)
þ
and CEC on the bottom X-axis); Fig. 3 presents the global- on the bottom X-axis.
chemistry parameters (pH and EC on the top X-axis and WSOC The sum of exchangeable cations often exceeded the total
on the bottom X-axis); and Figs. 4, 5 and 7 show the chemical charge of the clay (CEC), as shown in Appendix A (Tables A.1.4,
(2011), doi:10.1016/j.wasman.2011.11.008
Fig. 2. Sheet-silicates content, specific surface area (SSA) and cationic-exchange capacity (CEC) profiles of (a) L1B1, (b) L1B2, (c) L2B1, (d) L2B2, (e) L3B1 and (f) L3B2.
A.2.4 and A.3.4). In all cases, this result was caused by the high did not correspondingly increase. The higher the carbonate mineral
concentrations of Ex_Ca2+ because the other exchangeable cations content of the samples observed, the higher the measured
(2011), doi:10.1016/j.wasman.2011.11.008
Fig. 3. pH, electrical conductivity (EC) and water soluble organic carbon (WSOC) profiles of (a) L1B1, (b) L1B2, (c) L2V1, (d) L2B2, (e) L3B1 and (f) L3B2.
concentration of Ex_Ca2+ and the more the sum of exchangeable and their crystal size (Dohrmann, 2006; Dohrmann and Kauf-
cations exceeded the CEC (Appendix A). Therefore, these values hold, 2009).
were attributed to the dissolution of carbonate minerals during
the analysis and not to the extraction of exchangeable cations. 4.3.1. L1
This is a common analytical artifact that cannot be directly re- To characterize the different materials under the landfills,
solved because it depends on the nature of the calcium minerals sheet-silicate content, SSA and CEC were studied along the profiles.
(2011), doi:10.1016/j.wasman.2011.11.008
with depth in L1B1 (from 8.6 to 9.2) and L1B2 (from 8.5 to 9.7).
This increase in pH is associated with the evolution from a shallow
zone, which is especially affected by the landfill leachate, to a nat-
ural carbonate-clay material that determines the chemistry at
increasing depths. WSOC becomes attenuated at a <0.19-m depth,
with <150–100 lg/g in L1B1 and L1B2 (Fig. 3a and b). Lower values
than these were measured at 0.013 m in L1B3. In fact, this borehole
reaches background levels within the first few centimeters and as-
sumes average values with respect the rest of the analyzed param-
eters that are very close to the background values of L1B1 and
L1B2. The EC is attenuated at 1.55 m in L1B1 and at 0.75 m in
L1B2, with values of 0.8 and 0.4 mS/cm, respectively (Fig. 3a and
b). The EC from L1B3 samples is always <0.5 mS/cm.
The attenuation of EC is related to the decrease in the major
ions of the landfill substratum (Sol_Na+ and Sol_Cl, Fig. 4). These
ions are attenuated in each borehole at the same depths as the EC.
Indeed, both ions are the main soluble components of the landfill
leachate (Table 2). In contrast, relatively low amounts of ammo-
nium and organic components are present, and these are signifi-
cantly reduced or diluted in the studied profiles (Fig. 3a and b,
Fig. 4). Regarding the exchangeable cations, high concentrations
of Ex_Na+ were measured in the shallowest samples: 7.8 and
3.3 cmol(+)/kg in L1B1 and L1B2, respectively. These concentra-
Fig. 4. L1B2 ion-profiles. tions fall to background values of 1.4 (at 1.55 m in L1B1) and 0.2
(at 1.55 m in L1B2) cmol(+)/kg. The attenuation depth for Ex_Na+
is the same as that for the soluble ions (1.55 m) in L1B1. In the case
of L1B2 (Fig. 4), the Ex_Na+ is attenuated at a greater depth
(1.55 m) than the soluble ions (0.75 m). As a result of the unpol-
luted nature of L1B3, both soluble and exchangeable ion values
have low concentrations along the entire profile (<5 mmol/L for
Sol_Na+ and <0.2 cmol(+)/kg for Ex_Na+).
The L1B1 samples have higher salt concentrations than the L1B2
samples, whereas those of L1B2 are higher than those of L1B3. As
indicated in Section 2.1, L1B1, L1B2 and L1B3 have decreasing
waste thicknesses and leachate heads from L1B1 (bottom of the
slope) to L1B3 (top of the slope). Indeed, L1B3 presents the charac-
teristic properties of the undisturbed clay substrata.
4.3.2. L2
Sheet-silicate content, SSA and CEC in L2 are 48 ± 18%,
36.4 ± 19.8 m2/g and 9.2 ± 3.7 cmol(+)/kg, respectively. Despite
having a higher sheet-silicate content and, in particular, a higher
SSA than the L1 substratum, the CEC is much lower (Fig. 2a, b, c
and d). The L2 CEC values exhibit the least variation along the ver-
tical profiles among the three locations. L2B1 shows high values of
sheet silicates, SSA and CEC in the first 0.11 m, which quickly
diminish. Next, at 3.55 m, the maximum values of these parame-
ters are observed (Fig. 2c). In L2B2, these variables increase to a
depth of 1.15 m and then decrease at a more rapid rate to a depth
Fig. 5. L2B1 ion-profiles.
of 2.32 m, where they become constant (Fig. 2d). The clay-mineral
distributions in L2 show two heterogeneous, less clayey layers
(Fig. 2c and d). The first layer begins from the point of contact
and rapidly evolves to a more clayey section (from 63 to 74% sheet
These parameters are positively related and contribute to the silicates in L2B1 and from 44 to 54% sheet silicates in L2B2). This
attenuation of pollutants. more-clayey and narrow section is immediately followed by a de-
The average values of sheet silicates, SSA and CEC of L1 sub- crease in sheet-silicate contents that affects greater thicknesses
strata are 47 ± 17%, 20.5 ± 9.8 m2/g and 16.7 ± 6.9 cmol(+)/kg, (3.4 m in L2B1 and 1.1 m in L2B2). At these depths (3.5 and
respectively. The L1B1 borehole shows an increase in these param- 1.15 m in L2B1 and L2B2, respectively), a clay-rich material ap-
eters with depth, whereas in L1B2, the values increase from 0 to pears again (81% sheet silicates in L2B1 and 60% sheet silicates in
0.75 m, beyond which they begin to decrease (Fig. 2a and b). In L2B2).
the case of L1B3, sheet-silicate content, SSA and CEC decrease The two boreholes of L2 show pH values of approximately
down to 0.63 m, then increase down to 1.45 m; from this depth on- 8.9 ± 0.1, with the highest pH found at the point of waste contact
ward, the material-characterization parameters stabilize at 50%, (Fig. 3c and d). WSOC attenuation is observed at 0.95 and 0.68 m
25 m2/g and 13 cmol (+)/kg, respectively. for L2B1 and L2B2, respectively, with background values of
The three boreholes of L1 present a rather homogeneous pH 50 lg/g (Fig. 3c and d). Unlike in L1 (in which the EC is attenuated
(Fig. 3a and b), with values of approximately 8.8 ± 0.3 that increase after WSOC), in L2, EC attenuation (1.1 mS/cm) took place at 0.25
(2011), doi:10.1016/j.wasman.2011.11.008
Fig. 6. (a) Lineal correlation between Sol_NHþ

4 and water soluble organic carbon (WSOC). (b) L2 sulphate-profiles for B1 and B2 boreholes.
In L2B1, the same increase that is observed for WSOC (Fig. 3c)
can be observed for NH4+ (Fig. 5), indicating that the main origin
of the NH4+ of the substrate comes from the organic matter, as
shown in Fig. 6a for L2 and L3. Ex_Na+ and Ex_NH4+ exhibit similar
behaviors along the depth profiles. Values of 3.7–6.5 cmol(+)/kg
were measured in L2B1 and L2B2, respectively, at the point of
waste contact for Ex_NH4+ and of 1.5 cmol(+)/kg for Ex_Na+. The
average value of the total CEC at the point of waste contact is
10–14 cmol(+)/kg for L2B1 and L2B2, respectively (Fig. 2c and d);
these values are typical for the illitic mineral (Hang and Brindley,
1970) that composes the natural clay under this landfill (Table 3).
In this case, at the point of waste contact, the cation-exchange
complexes of the sheet silicates are mostly saturated with
+
Ex_NHþ 4 and Ex_Na (Appendix A: Table A.2.4). In contrast, after
the attenuation depth of 1 m, the sum of these monovalent cations
is less than 1 cmol(+)/kg. Although values as low as 4 cmol(+)/kg of
total CEC were measured, at these depths, Ex_Ca2+ and Ex_Mg2+
dominate the exchange complex (Appendix A: Table A.2.4). The
L2B1 borehole shows a relative increase in Ex_Na+ at 3.5 m
(Fig. 5). This increase is found at the same position as the maxima
of sheet-silicate content, SSA and CEC (Fig. 2c) and reflects the
retention capacity of the clay minerals.
At the point of waste contact, the Sol_NHþ 4 concentration is
much higher than that of Sol_Na+, whereas at depths of 3–4 m,
Fig. 7. L3B1 ion-profiles. the Sol_NHþ 4 concentrations are very low compared to those of
Sol_Na+. Furthermore, the Sol_Na+ decreases by 79% relative to
its concentration at the point of waste contact, and the Sol_NHþ 4
and 0.23 m for L2B1 and L2B2, respectively, i.e., approximately decreases by 98%. This indicates that NHþ 4 is a typical signature
0.70–0.45 m before the attenuation of WSOC. This is explained of the leachate.
by the fact that the initial L2 EC values (2.5 mS/cm) are much lower The lower quantity of sulfate in the first 0.35 and 0.68 m of L2B1
than those in L1 (7–16 mS/cm). This suggests that WSOC, which is and L2B2, respectively, (Fig. 6b) coincides with the attenuation of
significantly higher in L2 (540–750 lg/g) than in L1 (510–515 lg/g), the organic matter front (Fig. 3c and d). From these depths onward,
makes a small contribution to the value of the EC compared to the WSOC is attenuated, and sulfate concentrations begin to increase.
influence of inorganic soluble salts. WSOC increases locally in L2B1 The oxidation of organic matter in the first centimeters may pro-
at 2.5 m (Fig. 2c). At the same depth, the minimum sheet-silicate vide electrons to reduce the sulfate to sulfide. This reaction is com-
content and specific-surface values were found (Fig. 2c). This mon in the methanogenic stage of a landfill, when sulfate
layer of material is presumed to have a higher permeability and concentrations decrease in response to microbial reduction under
lower retention capacity than the materials that are found above strict anaerobic conditions (Kjeldsen et al., 2002; Lyngkilde and
(0–0.5 m with an average K of 3 109 m/s) and below (>3.5 m). Christensen, 1992a, b).
Thus, the transport of pollutants related to lateral hydraulic flows Similar depth evolution parameters and values were measured
cannot be disregarded. at both boreholes, though L2B2 has a higher ion concentration than
The attenuation of both soluble and exchangeable cations L2B1, in the shallowest samples. This finding is consistent with the
(Fig. 5) is observed at 0.95 and 1.15 m in L2B1 and L2B2, respec- thicker waste layer of L2B2 relative to that of L2B1 (Table 1) and
tively. Although the ions in L2B2 extend further than the WSOC, with the longer attenuation distance of L2B2 relative to that of
at the point at which the WSOC was attenuated (0.68 m), these L2B1. Nevertheless, an unknown local change in the nature of
ions are reduced by >90% in L2B2. waste may have an additional influence.
(2011), doi:10.1016/j.wasman.2011.11.008
4.3.3. L3 Table 5
L3 shows the highest values of sheet silicates, SSA and CEC of the The principal components after the Kaiser Varimax rotation.
three substrata, with averages of 75 ± 25%, 65.7 ± 30.7 m2/g and PC Variance (%) Variables (the correlation)
25.1 ± 15.7 cmol(+)/kg, respectively. However, the variation in the Negative correlation Positive correlation
sheet silicates and the SSA along its profiles is also the highest, i.e.,
1 21.711 Quartz (0.882) Sheet silicates (0.919)
the difference between the maximum and minimum values is higher Na-Feldspar (0.614) Ex_Mg2+ (0.918)
in L3 than in the other landfills. L3B1 has high values for both param- K-Feldspar (0.566) SSA (0.877)
eters along the profile to 3.3 m, where they drop under 50% and are pH (0.553) h (0.819)
then found in deeper samples (Fig. 2e). Likewise, CEC undergoes a CEC (0.814)
2 20.869 Sol_NHþ 4 (0.974)
slight decrease beginning at 1.6 m. These high initial values of sheet
Alk (0.966)
silicates, SSA and CEC in L3B1 are only present in L3B2 to 1.7 m. Be- +
Sol_K (0.963)
neath 1.7 m, they diminish by more than 60%, remaining constant in Ex_NHþ 4 (0.941)
deeper zones (Fig. 2f). The minimum values are found in the first Ex_K+ (0.868)
0.05 m of both boreholes as a result of possible mixtures with non- WSOC (0.818)
3 20.233 EC (0.965)
clayey materials (Fig. 2e and f).
Sol_Na+ (0.962)
Samples from this landfill have pH values of approximately Sol_Cl (0.953)
8.5 ± 0.2. L3B2 shows a small increase in pH (8.3–8.9) toward the Ex_Na+ (0.935)
deepest samples (Fig. 3f). EC and WSOC at the point of waste contact WSIC (0.778)
are higher in L3B1 (2 mS/cm and 1017 lg/g) than in L3B2 (1.3 mS/ Calcite (0.728)
4 6.451 Ex_Ca2+ (0.761) Na-Feldspar (0.564)
cm and 430 lg/g), but their attenuation occurs at similar depths in
5 6.157 Dolomite (0.692) Sol_Mg2+ (0.633)
L3B1 and L3B2. EC reaches background values (0.4–0.7 mS/cm) at Eh (0.529)
1 m and WSOC (background values of 52–130 lg/g) at 0.5 m 6 5.328 Sol_Ca2+ (0.727)
(Fig. 3e and f). This depth corresponds to a great increase in the pres- Sol_SO2
4 (0.720)
ence of clay (90% sheet-silicate contents; Fig. 2e and f). The higher
h: moisture, Ex_cation: exchangeable cation, CEC: cationic-exchange capacity, EC:
(almost double) EC in L3B1 when compared to L3B2 (Fig. 3e and f) electrical conductivity, Sol_ion: soluble ion, Alk: alkalinity, Eh: redox potential.
is related to the concentration of soluble ions (Fig. 7).
Ammonium is the predominant soluble cation (50–94 mmol/kg) grouped by each PC and the degree of correlation within the
and is complemented mostly by organic acid anions and bicarbonate variables in each component (indicating the contribution of the
alkalinity (Appendix A: Table A.3.3). The attenuation of Sol_NHþ 4 variable within the PC). Thus, PC 1 explains 21.71% of the variance
(4.1 mmol/kg at 1.60 m in L3B1 and 0.51 mmol/kg at 0.25 m in and is associated with 9 variables instead of the original 28. This PC
L3B2) follows the same pattern as EC attenuation. Sol_Na+ is atten- is positively affected by moisture, Ex_Mg2+, CEC, sheet-silicate content
uated at 0.34 m (12.3 mmol/kg) and 0.44 m (10 mmol/kg) for L3B1 and SSA and negatively affected by pH, quartz, sodic-feldspar and
and L3B2, respectively. Ex_NHþ 4 diminishes from 7.2 to potassic-feldspar.
0.5 cmol(+)/kg at 2.2 m in L3B1 and from 4.8 to <0.1 cmol(+)/kg at The focus of the analysis is on PCs 1, 2 and 3 because they account
0.44 m in L3B2. In L3B2 between 0.10 and 1 m, the sheet–silicate for more than 60% of the total variance. PC 1 is formed by the type of
content is >92%, and the total CEC ranges between 45 and minerals and physicochemical parameters such as SSA, Ex_Mg2+, pH
50 cmol(+)/kg (Fig. 2f). These highly sorptive and clay-grade proper- and CEC. PC 1 is therefore related to geological information. PC 2 is
ties explain how Ex_NHþ þ
4 and Sol_NH4 are attenuated at very short affected by WSOC and the soluble and exchangeable species of
depths compared to L3B1, which has 80–90% sheet silicates and ammonium, potassium and alkalinity, representing primarily the
20–30 cmol(+)/kg in total CEC (Fig. 2e). Both clayey materials con- organic charge on the landfill substratum. PC 3 is the result of the
tain a significant proportion of smectite (the mineral that mostly combination of EC, sodium, chloride, WSIC and calcite, which ex-
contributes to CEC) and show very high specific-surface values plains inorganic soluble components and inorganic carbon. These
(80–90 m2/g), which is consistent with the presence of montmoril- PCs have similar variances because all of them group a similar num-
lonite smectites (Dogan et al., 2006). ber of correlated original variables, whereas the other PCs are
L3B1 was drilled in a lower part of a slope than L3B2 (Sec- formed by a lower number of correlated variables.
tion 2.1), receiving greater quantities of leachate and supporting
more waste than L3B2. This is consistent with the fact that L3B1
has higher salt concentrations than L3B2. 5. Discussion
4.4. Principal component analysis 5.1. Leachates
PCA reduced the dimensionality of the data by diagonalizing the The interaction between a leachate and a geological barrier de-
correlation matrix of the variables (Appendix B: Tables B.1 and B.2) pends on a variety of factors, including leachate composition,
and transforming the 28 variables into 28 uncorrelated (orthogo- which varies with (1) landfill age (i.e., the degree of waste stabil-
nal) variables called principal components (PCs) (Appendix B: ization), (2) landfill technology, (3) climate, (4) waste composition
Table B.3). According to the criterion of Cattell and Jaspers and (5) geological location (Chian and DeWalle, 1976; Christensen
(1967), 6 PCs out of the 28 were selected (Appendix B: Fig. B.1). et al., 2001; Renou et al., 2008; Vadillo et al., 1999).
These six PCs explain more than 80% of the variance. The loadings The three landfills are all mature (more than 10 years old) and
of the 28 variables on the 6 significant PCs calculated by PCA are use comparable containment technologies (no synthetic polymer-
shown in Appendix B: Table B.4. composite liners). Many studies have shown a relationship
A Varimax rotation was applied to highlight the participation of between the landfill age and the leachate chemical composition
the variables that show higher contributions and to diminish the (Kulikowska and Klimiuk, 2008; Nanny and Ratasuk, 2002; Renou
variables that show lower contributions. These calculations helped et al., 2008; Salem et al., 2008; Shouliang et al., 2008; Tatsi and
us to associate the correlated variables and to reduce the original Zouboulis, 2002). The pH increases with landfill age, whereas the
large number of variables without losing too much information. chemical and biological oxygen demand (COD and BOD, respec-
The last column of Table 5 summarizes the variables that were tively) and low-molecular-mass organic acid levels (LMMOAs)
(2011), doi:10.1016/j.wasman.2011.11.008
undergo a rapid decrease during the first five years. Low BOD/COD than MW (Barton et al., 1985). In contrast, L2 and L3 received
ratios are typical of final anaerobic-methanogenic landfill stages mainly MW, which is related to the higher concentration of organic
(Banar et al., 2006; Chofqi et al., 2004; Ehrig, 1988; Renou et al., matter (WSOC) and lower concentrations of metals, than L1L
2008; SWANA, 1997; Taylor and Allen, 2006). Electrical conductiv- (Table 2). Thus, the quality of waste is the factor that most influ-
ity (EC) and dissolved solids (DS) also decrease with landfill age; ences the pollution profiles.
however, as a result of the fluctuation of dry and wet seasons, these
reductions occur over longer periods of time than do changes in 5.2. The mineralogy of landfill substrata
COD, BOD or LMMOA. Table 6 shows the average values of leachate
chemical parameters obtained from 25 different studies. The three locations present the same type of non-sheet-silicate
BOD and COD were not measured in the landfill leachates; minerals but in different proportions. Quartz is the dominant min-
therefore, no conclusions regarding the BOD/COD ratios can be eral in all cases, found in every type of environment because it is
made. The pH of L2L is consistent with the average pH calculated very resistant to erosion, weathering, transport and sedimentation.
for mature landfills (>10 years old), whereas L1L and L3L leachates The L1 substratum is made up of a significant concentration of car-
show pHs that are slightly less basic (Tables 2 and 6). This differ- bonates (20%), especially calcite, whereas L2 and L3 have lower
ence may be result from the continuous landfill operation that carbonate concentrations (1–3%). Calcite is relatively easy to dis-
causes the mixing of old and new leachates. Nevertheless, older solve at slightly acidic pH, releasing calcium and bicarbonate to
landfills tend to have leachates with higher pHs. Landfills L1 and the solution and increasing the porosity and, consequently, the K.
L2 (23 and 24 years old, respectively) have higher leachate pH val- However, because soil pHs were maintained under alkaline condi-
ues (7.20 and 7.90, respectively) than L3L (13 years old and with a tions in the three landfills (8–9), this potential effect was not de-
pH value of 6.70). The slightly acidic pH of L3L indicates that there tected. This buffering capacity seems to be favorable for the
are some areas in the landfill where the acetogenic stage has not performance of the landfill substrata with respect to heavy metal
yet been completed. This is common in landfills, where acetogenic migration, for instance. In addition, at these pH values, some trace
and methanogenic stages usually occur simultaneously at different heavy metals (such as those of Zn, Cu and Ni) and ions (Fe, Mn) are
locations of the same landfill (Kjeldsen et al., 2002). precipitated in the presence of carbonates (Mostbauer, 2003).
Over time, and as the stabilization of waste passes from the aer- The sheet-silicate minerals in the three substrata are illite,
obic to the methanogenic stage, Eh decreases. During methanogen- smectite and chlorite; L2 also presents some kaolinite. The differ-
esis, CH4 is increasingly produced, indicating an important ence between the locations is the proportion of illite and smectite
reducing environment with Eh < 0 mV (Banar et al., 2006; Taylor (Table 3). The ratios of illite to smectite in L1, L2 and L3 are 1.8, 5
and Allen, 2006). This is not reflected in Table 6 as a result of the and 3.5, respectively. L1 and L3 have similar smectite content, but
limited number of data found during the literature review for ma- L3 has double the illite content of L1. The clay minerals differ in
ture landfills (eight), which do not provide a consistent statistical their retention capacity, exhibiting a more or less charged surface
base. Furthermore, if large volumes of water percolate through to catch the dissolved contaminants in the leachates. Thus, the
the landfill (e.g., rainfalls) and substrata have low permeability, minerals that possess desirable characteristics for pollutant reten-
Eh increases in response to the dissolved oxygen and oxidants pro- tion (i.e., high SSA and CEC) conform to the following order: smec-
vided by the water (Lee et al., 2006). tite > illite P chlorite kaolinite (Bergaya et al., 2006).
Regarding the climate and waste composition, L1 has a higher SSA (L3 > L2 > L1) varies mainly as a function of the sheet-sili-
rainfall than L2 and L3, and this produces greater quantities of cate content. In general, it was observed that low values of SSA
leachates. In fact, L1L has a lower WSOC and ammonium concen- and of sheet-silicate led to attenuation at greater depths than those
tration than do the other leachates, which is likely related to the observed for high values of SSA and sheet-silicate contents.
presence of higher amounts of leachate that is more diluted as a re-
sult of the high volumetric flow. However, L1L has higher concen- 5.3. Leachate infiltration: pollution profiles and attenuation depths
trations of sodium and chloride than do the other landfills, which
corresponds to the mixed urban and industrial waste that is re- EC, WSOC and the main soluble-ion concentration of the corre-
ceived by L1 because industrial waste possesses less organic charge sponding leachate were used to define a general attenuation depth
Table 6
The average chemical compositions of characteristic parameters of leachates for different landfill ages: a review.
Landfill age pH EC (mS/cm) SS (mg/L) DS (mg/L) NH4+ (mg/L) Cl (mg/L)

New 7.0 ± 0.9 15.6 ± 7.7 1888 ± 1402 16204 ± 10882 2692 ± 3068 2966 ± 2213
No. samples 45 23 11 23 25 28
Medium 7.4 ± 0.6 17.9 ± 10.0 772 ± 287 32260 ± 26770 1267 ± 1476 3449 ± 3194
No. samples 35 22 3 21 33 25
Mature 7.7 ± 0.9 13.2 ± 9.7 704 ± 685 6804 ± 8572 644 ± 810 3970 ± 3236
No. samples 35 17 9 9 27 17
Landfill age T (°C) Redox (mV) BOD (mg O2/L) COD (mg O2/L) BOD/COD
New 19.0 ± 5.9 60.1 ± 80.4 13001 ± 10672 25150 ± 20944 0.49 ± 0.30
No. samples 20 22 23 24 23
Medium 22.8 ± 7.6 85 ± 48.3 2621 ± 5143 7514 ± 8747 0.67 ± 1.79
No. samples 21 20 16 39 16
Mature 16.1 ± 6.5 208 ± 152.0 2181 ± 4364 6409 ± 11125 0.24 ± 0.21
No. samples 8 8 33 37 32
EC: electrical conductivity, S.S: suspended solids, D.S: dissolved solids, T: temperature, BOD/COD: biological/chemical oxygen demand.
The landfill age classification is based on Renou et al. (2008): New: <5 years, Medium: 5–10 years, Mature: >10 years.
Compiled from Banar et al. (2006), Cecen and Cakiroglu (2001), Chofqi et al. (2004), Depountis et al. (2009), El-Fadel et al. (2002), Kulikowska and Klimiuk (2008), Lobo and
Tejero (2007), Marttinen et al. (2003), Meju (2000), Mohammadzadeh et al. (2005), Mor et al. (2006), Morillas et al. (2009), Nanny and Ratasuk (2002), Owen and Manning
(1997), Renou et al. (2008), Salem et al. (2008), Sanchez-Chardi and Nadal (2007), Shouliang et al. (2008), Spagni et al. (2007), Statom et al. (2004), Swati et al. (2008), Tatsi
and Zouboulis (2002), Tejero et al. (1991), Vadillo et al. (1999), Zairi et al. (2004).
(2011), doi:10.1016/j.wasman.2011.11.008
at which most of the contaminants became naturally attenuated by the low content of organic charge, which accelerated the degrada-
the geologic barrier. The results are organized by landfills and tion processes of organic matter (Allen, 2001). The organic front
boreholes in Table 7 and include the initial and background values (WSOC) is generally attenuated at a shorter distance (Table 7) than
and the percentage decrease. These data show, in general, that the inorganic front (EC and dominant ion). This is consistent with
these natural clay layers located under the landfills represent an the rapid decrease of organic components in leachate, resulting
effective barrier to the migration of leachate contaminants, in from naturally induced organic matter degradation, compared to
agreement with other studies (Bellir et al., 2005; Chen et al., the slower decrease of EC and DS (Table 6).
2005; Frascari et al., 2004; Hermanns Stengele and Plötze, 2000; The attenuation of all ions in L2 occurs at the same depth,
Joseph et al., 2003; Rowe et al., 1995; Techer et al., 2001; Thornton whereas in L1(B2) and in L3, the cation that dominates the
et al., 2001). exchangeable sites migrates further than the soluble cation
The average data (Table 7) show that these natural clayey layers (Table 7). This is related to the high smectite content in both land-
located under the landfills represent a good barrier to the migra- fills (Table 3), a mineral that provides more positions for retaining
tion of the main leachate soluble contaminants, which in general cations in their negatively charged interlayer. As a consequence,
terms, become attenuated in 0.2–2.2 m after 9–24 years of waste the presence of characteristic cations in exchangeable sites can
deposit. These depths are similar to the ones registered for Na+ be taken as a reliable signature of the leachate penetration.
and Cl (up to 1.3 m) under a 15-year old MW landfill in Yanful The main difference between boreholes of the same landfill is
et al. (1988); for Na+, Cl and WSOC (1 m) also under a 15-year related to the waste thickness: the greater the waste thickness
old MW landfill in Quigley et al. (1987) and for Cl (>0.83 m) and (Table 1), the higher the parameter values (Table 7). In some cases,
volatile organic compounds (0.15 m) under a 5-year old hazardous waste-column thickness is also positively related to a deeper atten-
landfill in Johnson et al. (1989). In all cases, the substrata were nat- uation depth. In other cases, the attenuation depths are more clo-
ural clays. Lake and Rowe (2005) also presented short attenuation sely related to the different mineralogies and physical–chemical
depths in the underlying compacted clay of a faulty geomembrane properties of the substrata. In general, the differences between
component of the composite liner system, during 14 years. In addi- the attenuation depths of EC, WSOC and ions within the boreholes
tion, they confirmed their results with a contaminant transport of the same landfill are not significant, except for the ions in L3
modeling. On the other side, deeper depths in clayey soils were (1.6–2.2 m in L3B1 and 0.25–0.44 m in L3B2). L3B1 has a deeper
estimated by Munro et al. (1997) (Cl > 6 m, Na+&WSOC > 2 m), layer of high SSA and sheet silicates that have retained cations at
denoting the dominance of diffusion transport over advection greater depths than L3B2 (Fig. 2e and f). In spite of this, L3B2 has
and a non-fractured material within the three substrata presented effectively attenuated the cations because the defined attenuation
in this paper. depths (Table 7) are shallower than those of the clay-rich material
The three natural clay layers presented a zone at a shallow (Fig. 2f). This case demonstrates the importance of implementing a
depth at which the proportion of clay minerals was low, followed high-quality mineral barrier.
by a sharp increase in sheet silicates with depth (Fig. 2). This find- The concentrations of the pollutants measured in the front be-
ing is presumably a result of the sands and silts deposited as tail- low the landfills are expected to be proportional to the main com-
ings from the previous clay quarry activities. The leachates may ponents measured in the leachate; however, the L2 front breaks
have been transported laterally through these heterogeneous from the anticipated correlation with regard to EC values. Taking
layers. This would affect the total amount of leachate potentially into account the fact that its analyzed leachate (L2L) has the high-
infiltrated through the underlined clay, but this does not invalidate est EC (Table 2), the samples under this landfill exhibit very low
the natural attenuation observed as a function of depth. The ana- conductivity (six times lower than that of the L1 samples, Fig. 3).
lyzed parameters become attenuated after penetrating the more This may be explained by the lateral migration of solutes through
clayey material (70% of sheet silicates in L1, 75% in L2B1, 60% in the poor clayey material through the uppermost detected in this
L2B2 and 90% in L3). That is not the case for the WSOC in L1, which substratum. A more detailed spatial study must be performed to
was rapidly attenuated through the less clayey material (30–40% of confirm this possibility.
sheet silicates) before reaching the clay-rich substratum below. Finally, to compare the attenuation capacity of the three sites
This finding is explained by the higher rainfall at this site and under similar conditions of time, leachate exposure or waste-column
Table 7
The initial and background values, attenuation depths, percentage decreases of EC, WSOC and characteristic ions of the pollution fronts by boreholes and by landfills.
Landfill Bore-hole EC WSOC Characteristic ion of the pollution front

Main components Initial background Depth Decrease Initial background Depth Decrease Ion Initial background Depth Decrease
in the leachate values values values
L1 B1 16 0.8 1.55 95% 520 130 0.18 75% Sol_Na+ 600 27 1.55 96%
12.97 mS/cm Ex_Na+ 7.8 1.4 1.55 82%
9850 mg Cl/L B2 7.2 0.4 0.75 94% 510 100 0.19 80% Sol_Na+ 270 15 0.75 94%
117 mg NH4+/L Ex_Na+ 3.3 0.2 1.55 94%
1260 mg WSOC/L
7700 mg Na+/L
L2 B1 2.5 1 0.25 60% 750 50 0.95 93% Sol_NHþ4
72 3 0.95 96%
31.00 mS/cm Ex_NHþ 3.7 0.1 0.95 97%
4
5700 mg Cl/L B2 2.5 1 0.23 60% 540 50 0.68 91% Sol_NHþ 90 3 1.15 97%
4
1786 mg NH4+/L 6.5 0.1 1.15 98%
Ex_NHþ4
1744 mg WSOC/L
L3 B1 2 0.7 1.00 65% 1070 130 0.50 88% Sol_NHþ4
95 4 1.6 96%
4.12 mS/cm Ex_NHþ 7.2 0.5 2.2 93%
4
269 mg Cl/L B2 1.3 0.4 1.00 69% 430 52 0.44 88% Sol_NHþ 50 0.5 0.25 99%
4
160 mg NH4+/L 4.8 <0.1 0.44 98%
Ex_NHþ4
3,360 mg WSOC/L
195 mg Na+/L
(2011), doi:10.1016/j.wasman.2011.11.008
Table 8
Diffusive flux attenuation capacities (Ac) for EC, WSOC and dominant leachate ions by time of leaching, ton of deposited waste and surface area of the landfill vessel for each landfill.
Substrata Age W Rd Ac
EC WSOC Sol_cat Ex_cat EC WSOC Sol_cat Ex_cat
L1 23 2.61 0.93 4.20 0.94 0.57 55.83 252.13 56.43 34.22
L2 24 0.68 2.51 1.16 0.93 0.94 40.58 18.85 15.10 15.34
L3 13 0.40 0.67 1.88 2.28 1.33 3.48 9.78 11.86 6.89
thicknesses, the following equation was developed and applied confidence regarding the values of thickness (depth) and K of the
for each indicative parameter of Table 7. The objective was to nor- natural liner under an urban landfill established by the Directive
malize the data to define a comparable diffusive flux attenuation 1999/31/EC (1999) (P1 m and 61.0 109 m/s). Because some
capacity (Ac) between landfills: of the leachates may migrate through preferential pathways in
the studied cases, these data may overestimate the attenuation
Ac ¼ Rd Y W; capacity of the materials. Nevertheless, taking the results of this
study into account, such conditions ensure waste retention for
where Rd (m1) is the ratio decrease per meter depth of the indica-
up to 24 years for the major soluble components of leachates when
tive parameter, averaged per landfill. This was calculated as (per-
the landfill leachate is collected.
centage decrease/100)/attenuation depth. Y (years) is the age of
the landfill at the time of sample collection. W (t/y/m2) is the quan-
tity of waste deposited per year and per unit of area. 5.4. The interpretation of the principal component analysis
Hence, the higher the Ac value, the better the barrier perfor-
mance of the substratum. In Table 8, the three landfill sites are All of the PC scores that corresponded to each analyzed sample
ranked from high to low Ac as follows: L1 > L2 > L3. The highest (Appendix B: Table B.5) were represented as pairs in a bivariate
Ac corresponds to the substratum with the lowest K plot (1 axis per PC) and were then differentiated according to the
(0.6 109 m/s). This high Ac coefficient in L1 is in response to three landfills. This procedure allowed for the observation that
the greatest amount of deposited wastes compared to the area of the geological PC 1 (Table 5) positively affects most of the samples
the landfill vessel within the three landfills, i.e., W (Table 8). This of L1 and L3 (i.e., they are situated on the positive side of the PC 1-
causes the natural material of L1 to reduce its EC per meter of axis), whereas L2 samples are distributed along the negative side
depth beyond that of L2 and ions per meter of depth beyond that (Fig. 8a). Therefore, L1 and L3 have more sheet silicates (because
of L3. L3 has the lowest Ac as a result of its shorter period of contact they have less quartz), moisture, CEC, SSA and Ex_Mg2+ (consistent
with the leachate pollution (it is 10 years younger than the other with the abundance of trioctahedral-Mg-sheet silicates in L3) than
landfills) and the minor quantity of waste mass per unit of area does L2. The fact that both L1 and L3 substrata decreased the
(Table 8).
A greater Ac value was expected for this landfill because it was
the one with the highest clay proportion with a high retention
capacity (Table 3). Because the age component is positively fac-
tored into the Ac equation, a future study would be necessary to
understand how the attenuation varies with time to generate con-
fidence the usefulness of the Ac parameter. Thus, if the capacity to
decrease the parameters per meter of L3 material does not change
after 10 years, its Ac for EC, WSOC, Sol_cation and Ex_cation will be
doubled. The defined coefficient may serve to compare old landfills
in the absence of precise hydrological and hydrochemical data, but
one must be careful not to distort the calculation with landfills of
very different ages.
When comparing the two landfills of similar age (L1 and L2),
even when L1 received almost four times as many tons of waste
per hectare than L2 and the initial ion values of L1 (i.e., ions mea-
sured at the shallowest samples) were considerably higher than
those of L2 (Table 7), there are no significant differences regarding
the Rd values of the soluble species between these landfills (Ta-
ble 8). Furthermore, the WSOC is more rapidly attenuated in L1
(diminishing 420% per meter) than in L2 (116% per meter) as a re-
sult of the lower initial WSOC and the higher precipitation in L1
than in L2, which increases the dilution and degradation of organic
pollutants.
Following a discussion of the attenuation depth data, a hypo-
thetical value for the K of the landfill substrata was estimated by
applying a simplified ratio that assumes a hydraulic gradient of 1
and neglecting the existence of diffusion transport. This K is the
average distance covered by the parameters, i.e., EC, WSOC, soluble
and exchangeable ions (1.01, 0.79 and 0.93 m), divided by the land-
fill age (23, 24 and 13 years). The resulting values (1.4 109,
1.0 109 and 2.3 109 m/s for L1, L2 and L3, respectively) are Fig. 8. Bivariate scatter plots of principal components scores from PC 1, 2 and 3
within an order of magnitude of the tested values. This provides (Appendix B: Table B.5).
(2011), doi:10.1016/j.wasman.2011.11.008
highest amount of WSOC, Sol_cation and Ex_cation at the shallow- Acknowledgements

est depth, whereas L2 showed a minor retention capacity (Rd in
Table 8), demonstrates that substrata with high values in the This work was supported by the Spanish Environmental Minis-
mineralogical and physicochemical parameters combined in PC 1 try (MMA: I+D+i A113/2007/3_02.6) in cooperation with Geotecnia
(Table 5) provide an effective barrier function. Therefore, the com- y Cimientos S.A. (GEOCISA) and the Centro de Experimentación de
ponents integrating this PC are proposed as the most relevant Obras Públicas (CEDEX).
parameters to be taken into account in defining the quality of opti-
mum clay barriers in future studies.
Appendices A and B. Supplementary data
PC 2, representing the organic related soluble species, influ-
ences L2 and L3 in the same way, but it does not affect L1
Supplementary data associated with this article can be found, in
(Fig. 8a and b) for any of the PC-crossed combinations. In contrast,
the online version, at doi:10.1016/j.wasman.2011.11.008.
L1 samples were affected positively by PC 3 (inorganic soluble
components) (Fig. 8b). Thus, both of these PCs (when they are plot-
ted together in a graph) distinguish L1 from L2 and L3 (Fig. 8b). References
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Departamento de Geología y Geoquímica

Tesis doctoral presentada a la Universidad Autónoma de Madrid, Facultad de

Madrid, Diciembre 2011.

Mercedes Regadío García. Director: Dr. Jaime Cuevas Rodríguez.

Difusión de contaminantes en vertederos antiguos construidos en terrenos arcillosos

Tesis doctoral, enero 2012

La tesis estará disponible en versión pdf en la página web de la biblioteca de Ciencias, de la

Dirección: Universidad Autónoma de Madrid

Teléfono: (+34) 91 497 48 00

Fax: (+34) 91 497 49 00

Página web: http://www.uam.es/departamentos/ciencias/geolgeoq/

Diffusion of pollutants in old

A thesis submitted to Autónoma University of Madrid, Faculty of Science,

Madrid, December 2011.

Mercedes Regadío García. Supervisor: Dr. Jaime Cuevas Rodríguez.

Diffusion of pollutants in old landfills built over clayey substrata

PhD thesis, January 2012

Adress: Autónoma University of Madrid

Telephone: (+34) 91 497 48 00

Fax: (+34) 91 497 49 00

Mercedes Regadío García.

La presente tesis no hubiera sido igual sin la orientación, comentarios y aclaraciones de

Asimismo, quiero agradecer a Isabel de Soto su predisposición a resolver mis dudas

Deseo destacar la colaboración del departamento de Química Analítica y Análisis

De forma especial, quisiera reconocer la labor social, ambiental y solidaria de Amigos

Z4V1: Cataluña landfill

L1: leachate of deionized water

Consequently, the long-term effectiveness of several geological barriers beneath MW landfills

Landfills, clays, depth profiles of parameters, natural attenuation.

La presente tesis investiga la respuesta a largo plazo de distintas arcillas naturales

En general, se ha analizado en detalle la eficacia a largo plazo de varias barreras geológicas

Vertederos, arcillas, perfiles de parámetros en profundidad, atenuación natural.

Vertedero Incineración Reciclaje

Gas del vertedero

Evolución de las concentraciones (sin escala)

Eh a pH 7: 400/500 300/200 200/100 -200/-300

Los siguientes vertederos más antiguos, se encuentran en la etapa anaerobia metanogénica o

AGV, CH3COOH(aq) + Oxidante  CH4(g) + CO2(g) + (NH3(g) + H2S(g)…) (1.9)

CO2(g) + 4H2(g) CH4(g) + 2H2O(l) (1.10)

350 Z1V1S1 Z5V1S1

Alcalinidad (mmol/kg) Alcalinidad (mmol/kg)

MO (mm altura pico) H (%)

Sheet silicates (%) Sheet silicates (%) Sheet silicates (%)

0.25 0.25 0.25

0.50 0.50 0.50

0.75 0.75 0.75

1.00 1.00 1.00

1.25 1.25 1.25

1.50 1.50 1.50

1.75 Z5V1S1 1.75 Z5V1S2 1.75 Z5V1S3

SHEET SILICATES (%)

-0.5 0.0 0.5 1.0

Smectite Illite Chlorite

SSA (m2/g) A2L3

Depth (m) 0.1

A2L1 Ratio A2L1 Ratio

52 Linear fit A2L4

Soil (Sandy loam)

APPENDIX I. SPANISH LEGISLATION

- Ley 11/1997, de 24 de abril, de Envases y Residuos de Envases. BOE 99, de 25-4-1997.

- Orden de 27 de abril de 1998 por la que se establecen las cantidades individualizadas a

- Real Decreto 782/1998, de 30 de Abril por el que se aprueba el Reglamento para el

- Resolución de 30 de septiembre de 1998, de la Dirección General de Tributos, relativa a la